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>f 

A GUIDE 



TO THE 



QUALITATIVE AND QUANTITATIVE 



ANALYSIS OF THE URINE 



DESIGNED FOR 



PHYSICIANS, CHEMISTS AND PHARMACISTS 



BY 

Br. C. NEUBAUEE 

Professor, Chief of the Agricultural- Chemical Laboratory, and Bocent in the Chejnical 
Laboratory i?i Wiesbaden 

AND 

J)r. J. YOGEL 

Professor of Medicine in the University at Halle 
i^ WITH A PREFACE BY 

y^^ Prof. De. K. FEESENIUS 



TRANSLATED FROM THE SEVENTH ENLARGED AND REVISED 
GERMAN EDITION BY 

elbeidge g. cutler, m.d. 

Physician to Out Patients at the iVafsaehusetfs General Hospital, Pathologist at the Boston City 
Hospital, and Assistant in Pathology in the Medical School of Harvard University. 

REVISED BY 

EDWAED S. WOOD, M.D. - 

Professor of Chemistry in the Medical School of Harvard University , ■ : p yr ' g ■l^'^^fo^ 

, Zyo.AIJlJCz 



v. :A. 1879 






NEW YORK 
WILLIAM WOOD & COMPANY 

1879 



> 



i\ 



R>'>i 



COPTKIGHT, 

1879, 
By William Wood & Co. 



New York: J. J. Little & Co., Printers 
10 to 20 As tor Place. 



PEEFAOE TO THE FIEST EDITION. 



Mr. C. Neubauer, assistant in my laboratory, having been 
requested by a number of the physicians of the city, has given 
them a series of lectures on the analysis of the urine, which 
has recently undergone complete remodelling, and is constantly 
assuming a greater importance. 

These lectures gave the first origin to this book. Since 
Neubauer has labored with great diligence on the basis of the 
newest investigations, and has himself tried all of the accepted 
methods, it will prove very welcome both to physicians and to 
pharmacists and chemists who aid them, and will prove a reli- 
able guide to urinary analysis. 

The publisher has spared neither cost nor pains in preparing 
the book ; all apparatus is illustrated by fine wood-cuts, and 
the appearances of the most important normal and abnormal 
constituents of the urine are depicted in truly excellent plates, 
so that the work is to be highly recommended in this respect. 

Prof. Dr. R. FRESENIUS. 
Wiesbaden, April 5, 1854 



PEEFAOE TO THE SEVENTH EDITION. 



In revising the present seventh edition of my Analysis of the 
Urine, I have honestly tried my best to take account of the 
progress of science. In the first three divisions, therefore, I 
have carefully added all reactions and methods which have 
been approved by myself or others. Among the new additions 
are the chapters on brenzcatechin, acetone, and the two patho- 
logical coloring matters discovered by Baumstark, urorubro- 
hsematin and urofuscohaematin. 

The fourth division, which treats of the accidental constitu- 
ents of the urine, has been considerably enriched. It is evi- 
dent, at first sight, how important are the physiological and 
pathological changes which substances undergo in their pas- 
sage through the system, and, therefore, we gladly see that a 
considerable activity has been developed in this part of urinary 
analysis during the last few years. 

Also the second part, which includes the methods of quanti- 
tative analysis, has been considerably enlarged. I mention 
the handy and delicate method of determining the specific 
gravity by the Mohr-Westphal balance, the Knop-Hiifner 
method of determining the urea, which is very good and easily 
performed in many cases, and also Bunge's modification of 
Bunsen's method for the same purpose, w^hich, according to re- 
cent experience, is found to be indispensable in many cases 
where Liebig's method failed. Also, I could not refuse a place 
to the new method of determining chlorine by Yolhard and 
Falk, which is not inferior to Mohr's in accuracy. In the op- 
tical estimation of sugar, I have considered, besides the polari- 
scope of Yentzke-Soleil, that of Wild, which has decided ad- 
vantages over the former, and admits of an accuracy which I, 

V 



vi PREFACE TO THE SEVENTH EDITION. 

at least, have been unable to attain with the apparatus of 
Ventzke-Soleil. Also, the estimation of sugar from the dif- 
ference in specific gravity before and after fermentation, will 
not be entirely unwelcome to many physicians who are not 
conversant with volumetric analysis, and who do not have the 
expensive optical apparatus at their command. Lastly, I men- 
tion the new method of determining iodine by Hilger, and the 
method of Salkowski for estimating uric acid. 

With regard to the formulas which I use, I have given them 
both in the old and new nomenclature, and have desig- 
nated the new atomic weights by large type and crossed capi- 
tals, to do justice to the old as well as the new friends of my 
book. 

I have received from different sources reprints of articles on 
the subject of urinary analysis, by which the review of the 
chemical, medical, and physiological current literature of the 
scattered material has been rendered essentially easier. I 
most heartily thank all who have aided me in this labor, and, 
at the same time, beg that they will be as kindly thoughtful in 
the future. 

May this new edition receive the same friendly acceptance 
and favorable criticism which has been its lot before. 

C. NEUBAUER. 
Wiesbaden, October, 1875. 



EEYISEE'S PEEFAOE, 



The want of a practical manual and suitable text-book upon 
the analysis of the urine in the English language has long been 
felt. This want has, during the past few years, been partly 
supplied by Dr. Tyson's excellent little " Guide to the Practical 
Examination of Urine," which, however, is not, and does not 
pretend to be, a complete manual upon urinary chemistry. The 
medical student and practitioner need to know something more 
than simply the methods which are required to obtain a knowl- 
edge of the chemical composition of the urine. They should 
be able to infer from it, to a certain extent, the general condi- 
tion of the patient whose urine is examined, and it is hoped 
that the present work may accomplish for the English reader, 
what the original has for the German student, viz., show him 
exactly what inferences may be drawn from a knowledge of 
the chemical composition of the urine, and in what way and 
to what extent a knowledge of the changes going on within the 
body may be learned by examining the urine. 

There is no book in the English language which treats the 

subject of urinary chemistry in so thorough and scientific a 

manner, and in none is the material so arranged as to be readily 

available to both student and practitioner. The separation of 

the book into two distinct parts, the first by Dr. Neubauer being 

strictly chemical, and the second by Dr. Yogel being chiefly 

medical, adds much to its value as a book of reference for both 

the chemist and physician. 

vii 



Viii REVISERS PREFACE. 

Since tlie former translation of Neubauer and Yogel, pub- 
lished by tlie New Sydenham Society in 1863, such vast pro- 
gress has been made in the domain of organic and physiological 
chemistry, that the original work has passed through four edi- 
tions, and the 1863 translation by, no means represents the 
present standpoint of urinary chemistry. The present (seventh) 
edition contains the most recent advances culled from the cur- 
rent literature of the day. 

Some difficulties have been met with in the translation, which 
all who have done the same kind of work can appreciate. The 
translation has been made as literal as possible to be consistent 
with clearness, and elegance of style has not been aimed at. 

Boston, 1879. 



TABLE OF COIN^TEII^TS. 



PAET FIRST. 

BY C. NEUBAUEE. 

DIVISION^ FIRST. 

I. 



PAGE 

§ 1. Physical and Chemical Properties of Normal Urine 3 

II. 

Normal Constituents of the Urine. 

A. Organic. 

§2. Urea 11 

A. Presence 11 

B. Preparation ' . . 13 

1. From Urine 13 

2. From Cyanate of Ammonium 14 

C. Microscopic Properties 14 

D. Chemical Properties 14 

Nitrate of Urea ' 17 

Oxalate of Urea 17 

Phosphate of Urea 18 

U. Detection 18 

§ 3. Kreatinin 19 

A. Presence 19 

B. Microscopic Properties 20 

C. Chemical Properties 20 

D. Preparation of the Chloride of Kreatinin from Urine 23 

E. Detection 24 

§ 4. Kreatin 25 

A. Presence 25 

B. Preparation 26 

C. Microscopic Properties 26 

D. Chemical Properties 27 

U. Detection 28 

§ 5. Xanthin 28 

A. Presence 28 

ix 



TABLE OF CONTEyTS. 

PAGE 

B. Microscopic Properties 29 

C. Chemical Properties 29 

D. Detection 31 

1. Xanthin 31 

2. Kreatinin 82 

3. Urea 32 

Appendix — Hypoxanthin (Sarkin) 33 

§ 6. Uric Acid. ." 35 

A. Presence 35 

B. Preparation 36 

1. From Human Urine 36 

2. From Excrement of Serpents 36 

C. Microscopic Properties 37 

D. Chemical Properties 37 

E. Detection 41 

§ 7. Oxaliiric Acid 43 

A. Presence 42 

B. Preparation 43 

C. Microscopic Properties 43 

D. Chemical Properties 44 

E. Detection 45 

§ 8. Hippuric Acid 47 

A. Presence 47 

B. Microscopic Properties 49 

C. Preparation 49 

D. Chemical Properties 50 

E. Detection 51 

Succinic Acid. 52 

§ 9. Phenol (Carbolic Acid, Phenylic Acid, Phenylic Alcohol) 55 

A . Presence 55 

B. Chemical Properties 56 

1. Taurylic Acid 57 

2. Damaluric Acid 57 

3. Damolic Acid 57 

Detection and Separation of the four Acids 58 

1. Collectively 58 

2. Individually 58 

C. Detection m Human Urine 59 

5 10. Urinary Coloring Matters 60 

I. Urobilin 60 

A. Presence 60 

B. Separation and Properties 60 

C. Occurrence in Normal Urine 62 

II. Urochrom 64 

A. P-reparation 65 

B. Properties 66 

III. Uroxanthin (Heller)— Indican (Schunk) 67 

A. Preparation , , 68 



TABLE OF CONTENTS. 



XI 



PAGE 

IV. Uroglaucin and Urrhodin G8 

(Indigo blue and indigo red.) 

a. Urrhodin (indigo red) G9 

h. Uroglaucin (indigo blue) 69 

A. Preparation by the Method of Sehunk 70 

B. Preparation by the Method of Kletzinsky and Keller 70 

C. Detection 71 

V. Uroerythrin 73 

YI. Black Urine 74 

§ 11. Kryptophanic Acid 74 

§ 12. B. Inorganic. 76 

§ 13. Chloride of Sodium 76 

A. Presence 76 

B. Microscopic Properties 77 

C. Chemical Properties 77 

D. Detection 79 

§ 14. Chloride of Potassium 79 

§ 15. Sulphates 80 

A. Presence 80 

B. Chemical Properties 80 

C. Detection 81 

§ 16. Acid Phosphate of Sodium 81 

A. Presence , 81 

B. Chemical Properties , 82 

a. Detection 83 

§ 17. Phosphates of Calcium and Magnesium 83 

Detection 84 

§ 18. Iron 84 

A. Presence. 84 

B. Chemical Properties 85 

C. Detection 85 

§ 19. Ammonium Salts 86 

Detection 87 

§ 20. Silicic Acid 88 

§ 21. Nitrates and Nitrites 88 

§ 22. Hydrogen Peroxide 89 

Detection in Urine 90 

III. 

Abnormal Constituents of Urine. 

§ 23. Albumen (Serum Albumen) 91 

A. Presence 91 

B. Preparation of Pure Albumen 91 

C. Chemical Properties 92 

D. Preparation of Albumen absolutely free from Salts by Diffu- 

sion 94 

E. Detection 95 



xii TABLE OF CONTENTS. 

PAGE 

§ 24. Supplement 97 

1. Fibrine 97 

2. Casein 98 

3. Albuminose 98 

4. Paralbumen and Paraglobulin 99 

Detection of Paraglobulin in Albuminous Urines 99 

5. Peptone 100 

Detection of Peptone in Albuminous Urines 100 

6. Nephrozymose 100 

§ 25. Urinary Sugar— Grape Sugar 101 

A. Presence 101 

B. Microscopic Properties 102 

C. Preparation of Chemically Pure Grape Sugar 102 

D. Chemical Properties 103 

a. Saccharate of Potassium 103 

h. Saccharate of Calcium 103 

c. Compound of Grape Sugar with Chloride of Sodium 103 

E. Detection lOG 

§ 26. Alkapton 114 

§ 27. Inosite 114 

A. Presence 114 

B. Microscopic Properties 115 

C. Chemical Properties 115 

D. Detection 116 

§ 28. Biliary Substances 117 

Biliary Coloring Matters 118 

A. Presence 118 

B. Preparation 118 

C. Chemical Properties 118 

a. Bilirubin (Cholepyrrhin) 118 

1). Biliverdin 120 

c. Biliprasin ■ 120 

d. Bilifuscin 121 

D. Detection 121 

§ 29. Biliary Acids 124 

1. Tauroeholic Acid 124 

2. Glycocholic Acid 125 

A. Chemical Properties 126 

B. Detection 127 

§ 30. Lactic Acid 130 

A. Presence 130 

B. Chemical Properties 131 

1. Lactate of Calcium 132 

2. Lactate of Zinc 132 

a Detection 132 

§ 31. Volatile Fatty Acids 134 

I. Formic Acid 134 

//. Acetic Acid 135 



TABLE OF CONTENTS. xiii 

PAGE 

III. Propionic Acid 135 

IV. Butyric Acid 138 

V. Baldrianic Acid 137 

Detection of the Fatty Acids 137 

§ 33. Benzoic Acid 138 

A. Presence 138 

B. Microscopic Properties 139 

C. Chemical Properties 139 

D. Detection 140 

§ 33. Fats 140 

A. Presence 140 

B. Microscopic Properties 141 

C. Detection 141 

§ 34. Sulphuretted Hydrogen 142 

§ 35. AUantoin 144 

A. Presence 144 

B. Preparation 144 

C. Microscopic Properties 145 

D. Chemical Properties. 145 

E. . Detection 145 

Alloxan 146 

§ 36. Leucin 147 

A. Presence 14T 

B. Microscopic Properties 147 

C. Chemical Properties 147 

D. Detection and Preparation 148 

§ 37. Tyi-osin 149 

A. Presence 149 

B. Microscopic Properties 149 

C. Chemical Properties 149 

D. Preparation 150 

E. Detection 153 

g 38. Oxymandel Acid 153 

A. Presence 153 

B. Detection and Properties 154 

§ 39. Brenzcatechin (Oxyphenic Acid) 155 

§ 40. Urorubrohaematin and Urof uscohaematin 156 

§ 41. Acetone, Alcohol, and Ethyldiacetic Acid 157 

Detection 157 

Derivation of the Acetone and Alcohol 158 

lY. 

§ 43. Urinary Sediments. 159 

I. Non-Organized Sediments. 163 

§ 43. Uric Acid 163 

§ 44. Urates 163 

1. Acid Urate of Sodium 164 

3. Acid Urate of Potassium 164 



xiv TABLE OF CONTENTS. 

PAGE 

3. Acid Urate of Ammonium 164 

4. Acid Urate of Calcium 165 

§ 45. Oxalate of Calcium 165 

A, Presence 165 

B, Microscopic Properties 166 

C, Detection. 167 

§ 46. Earthy Phosphates 168 

1. Ammonio-Magnesian Phosphate 168 

2. Phosphate of Calcium 169 

§ 47. Cystin 171 

A. Presence 171 

B. Microscopic Properties 173 



C. Chemical Properties 1 



D. Detection 173 

§ 48. Tyrosin 174 

§ 49. Xanthin (Hypoxanthin ?) 174 

II. Organiized Sediments. 

§ 50. Mucus and Epithelium 175 

§ 51. Blood 178 

A. Microscopic Properties 178 

1. Action of Water on Blood Corpuscles 178 

2. Action of Saline Solutions on Blood Corpuscles 179 

3. Action of Alkalies on Blood Corpuscles 179 

B. Detection 180 

1. The Urine contains Blood Corpuscles 180 

2. The Blood Corj^uscles are destroyed ; the Urine contains 

Methaemoglobin 180 

§ 52. Pus 183 

A. Microscopic Properties 183 

1. Action of Water on Pus Corpuscles 183 

2. Action of Acetic Acid on Pus Corpuscles 183 

3. Action of Alkalies on Pus Corpuscles 184 

B. Detection 184 

§ 53. Casts 185 

§ 54. Spermatozoa 186 

§ 55. Fungi. Infusoria 187 

Y. 

§ 56. Accidental Constituents of the Urine. 190 

I. Inorganic Siibsiances. 192 

A. Salts of the Heavy Metals 192 

Mercury 192 

Thallium 195 

Cadmium , 195 

B. Free Mineral Acids 196 

C. Salts of the Alkalies 196 

D. Salts of the Alkaline Earths 198 



TABLE OF CONTENTS, X7 

PAGE 

//. Organic Substances. 198 

A. Free Organic Acids 198 

B. Indifferent Substances 200 

C. Salts of the Organic Acids 203 

D. Organic Bases 204 

E. Coloring and Odorous Matters 209 



DIVISION SECOND. 

QUANTITATIVE ESTIMATIOi^S. 

§ 57. Estimation of the amount of Urine secreted in a given time 210 

§ 58. Specific Gravity 211 

1. By the Araeometer (Urinometer) 211 

2. With the Mohr-Westphal Balance 213 

3. With the Picnometer 214 

§ 59. Estimation of the Water and the Total Solids 21G 

§ 60. Estimation of the Non- Volatile Salts 221 

§ 61. Estimation of the Coloring Matters 222 

A. The Color Table 222 

B. Value of the Color Scales 223 

C. Application of the Method 224 

QUAKTITATIVE ESTIMATION" OF INDIVIDUAL SUBSTANCES. 

§ 62. Volumetric Analysis 225 

§ 63. I. Apparatus 226 

1. Graduated Pipette 226 

2. Mohr's Pipette ; 227 

3. Graduated Burette 229 

4. Graduated Cylinder 229 

§ 64. II. Performance 230 

§ 65. Estimation of Urea 232 

1. By Liebig's Method 232 

A. Principle 232 

B. Preparation of the Solutions 233 

1. Standard Urea Solution 233 

2. Standard Mercuric Nitrate Solution 233 

3. Baryta Solution 235 

C. Performance 235 

D. Modification of the Process and Corrections required by differ- 

ent circumstances 236 

1. The Urine contains more than 2 per cent, of Urea 236 

2. The Urine contains less than 2 per cent, of Urea 237 

3. The Urine contains Chloride of Sodium 237 

4. The Urine contains Albumen 239 

5. The Urine contains Carbonate of Ammonium 240 



xvi TABLE OF CONTENTS. 

PAGE 

2. By the Knop-Hiifner Method 243 

A. Principle 242 

B. Preparation of the Hypobromite of Sodium Solution 242 

C. Performance 242 

3. Bunsen's Method modified by G. Bunge 244 

§ 66. Estimation of Chlorine (Chloride of Sodium) 245 

I. Mohr's Method 245 

A. Principle 245 

B. Preparation of the Solutions 246 

1. Standard Nitrate of Silver Solution 246 

2. Potassium Chromate Solution 247 

C. Performance 247 

1. Modification in Urine containing Iodine and Bromine 248 

II. Method of J. Volhard and A. Faick 248 

A. Principle 248 

B. Preparation of the Solutions 249 

1. Standard Nitrate of Silver Solution 249 

2. Solution of Iron Oxide 249 

3. Standard Sulphocyanide of Potassium Solution 249 

C. Performance 250 

§ 67. Estimation of Phosphoric Acid 250 

A. Principle 250 

B. Preparation of the Solutions 252 

1. Standard Phosphoric Acid Solution 252 

2. Acetate of Sodium Solution 252 

3. Standard Uranium Solution 252 

C. Performance 253 

a. Estimation of the Total Phosphoric Acid 253 

J). Estimation of the Phosphoric Acid combined with the Alka- 
line Earths 255 

§ 68. Estimation of the Degree of Acidity 256 

A. Principle 256 

B. Preparation of the Solutions , 256 

1. Standard Oxalic Acid Solution 256 

2. Tincture of Litmus 256 

3. Standard Sodic Hydrate Solution 256 

C. Performance 257 

§ 69. Estimation of Sulphuric Acid • 257 

A. Principle 257 

B. Preparation of the Solutions 258 

1. Standard Chloride of Barium Solution 258 

2. Standard Sulphate of Potassium Solution 259 

C. Performance 259 

§ 70. Estimation of Sugar 261 

1. By Fehling's Method 261 

A. Principle 261 

B. Preparation of the Copper Solution 262 

C. Performance 262 



TABLE OF CONTENTS. Xvii 

PAGE 

2. By Knapp's Method 265 

A. Principle 265 

B. Preparation of the Mercuric Cyanide Sohition 265 

C. Performance 265 

3. By Circumpolarization 266 

A. With the Ventzke-Soleii Polarizer 266 

B. With the Polarizer of Wild 271 

4. By Fermentation 276 

5. From the Difference in Specific Gravity before and after Fer- 

mentation 277 

§ 71. Estimation of Iodine 278 

1. By Kersting's Method 278 

A. Principle 278 

B. Preparation of the Solutions 279 

1. Standard Iodide of Potassium Solution 279 

2, Standard Chloride of Palladium Solution 279 

C. Performance , 280 

2. By Hilger's Method 282 

3. Colorimetric Estimation by Struve's Method 283 

A. Principle 283 

B. Preparation of the Color Scale 283 

C. Performance 284 

§ 72. Estimation of Iron 285 

A. Principle 285 

B. Preparation of the Solutions 285 

1. Permanganate of Potassium Solution 285 

2. Ferrocyanide of Potassium Solution 286 

C. Performance 286 

§ 73. Estimation of Uric Acid 287 

1. By Precipitating with Hydrochloric Acid. . . , 287 

2. By Salkowski's Method. 290 

§ 74. Estimation of Kreatinin 291 

A. Principle 291 

B. Preparation of Chloride of Zinc Solution 291 

C. Performance 292 

§ 75. Estimation of Albumen 293 

A. Gravimetric Method 293 

B. By Circumpolarization 296 

1. Bcideker's Method 297 

2. Vogel's Optical Method 297 

3. Methods of Lang, Haebler, and Bernhardt 297 

4. Mehu's Method 298 

5. Liborius's Method 298 

6. Girgensohn's Method 299 

§ 76. Estimation of Calcium and Magnesium 299 

I. Estimation of the Calcium 299 

A. Principle. 299 

B. Preparation of the Solutions 299 

B 



xviii TABLE OF CONTENTS. 

PAGE 

1. Standard Hydrochloric Acid 299 

2. Standard Sodic Hydrate 300 

C. Performance 301 

II. Estimation of the Magnesium 302 

Gravimetric 302 

Volumetric 304 

III. Indirect Estimation of Calcic and Magnesic Phosphates 304 

§ 77. Estimation of Ammonia 306 

A. Principle 306 

B. Preparation of the Solutions 306 

1. Standard Sulphuric Acid 306 

2. Standard Sodic Hydrate 307 

C. Performance 307 

§ 78. Estimation of Ammonia and Potash with Platinic Chloride 308 

§ 79. Estimation of Potassium and Sodium 310 

A. Direct 310 

B, Indirect 311 

§ 80. Estimation of Carbonic Acid 312 

§ 81. Estimation of the Total Nitrogen 312 

A. Principle 314 

B. Preparation of the Solutions 314 

C. The Distilling Apparatus 315 

D. Performance 315 

§ 82. Estimation of the Fat 318 

§ 83. Estimation of Biliary Acids 318 

§ 84. Estimation of Indiean by Jaffe's Method 319 

§ 85. Estimation of Oxalic Acid 321 



DIVISIOlSr THIRD. 

I. 

86. Qualitative Analysis. 822 

87. Systematic Process for Detecting the Soluble Constituents 322 

11. 

88. Kecognition of Sediments under the Microscope. 329 

A. The Urine is Acid 330 

1. Amorphous 330 

2. Crystalline 331 

3. Organized 332 

B. The Urine is Alkaline.. 334 

1. Crystalline 334 

2. Amorphous 334 

3. Organized 334 

89. Preservation of Urinary Sediments 334 



TABLE OF CONTENTS. xix 
III. 

PAGE 

§ 90. QUAXTITATIYE ANALYSIS. 337 

IV. 

§ 91. Approximate Estimations. 344 

1. Estimation of the Earthy Phosphates by Beneke's Method. . 344 

2. Estimation of Calcic Oxalate by Beneke's Method 346 

§ 92. Analytical Experiments 347 

I. Table for Estimating the Total Solids from the Specific Gravity. 347 

II. Chlorine Analyses 348 

III. Phosphoric Acid Analyses 349 

IV. Sulphuric Acid Analyses 349 

y. Sugar Analyses 350 

VI. Kreatinin Analyses 351 

VII. Albumen Analyses 351 

VIII. Calcium Analyses 351 

IX. Ammonia Analyses 352 



PART SECOND. 

BY JULIUS VOGEL. 

Introduction » 356 

DIVISION FIRST. 

I. 

Changes in the Color, Appearance, and Odor of the Urine, . 363 

§ 93. Color of the Urine 363 

1. Normal 363 

2. Abnormal 365 

a. Essential 365 

1. Blood Pigment 365 

2. Biliary Pigment 366 

3. Indican 366 

4. Uroerythrin 368 

h. Accidental 368 

§ 94. Odor of the Urine 369 

§ 95. Transparency of the Urine 370 

II. 

§ 96. Chemical Reaction of the Urine. 370 

1. Acid 376 

2. Neutral or Alkaline 377 



XX TABLE OF CONTENTS. 

III. 

PAGE 

Unusual (Abnormal) Constituents. 378 

§ 97. Albumen 379 

A. Detection 379 

B. Significance 381 

1. Globulin or Paraglobulin 384 

2. Alkali Albuminate 384 

3. Peptone 384 

§ 98. Fibrine 388 

§ 99. Blood in the Urine 389 

A. Detection 389 

B. Importance 390 

§ 100. Dissolved Blood — Dissolved Ha3matoglobulin 392 

Importance 394 

§ 101. Fat 395 

A. Detection , 395 

B. Importance 396 

§ 102. Biliary Pigments 398 

§ 103. Biliary Acids 398 

§ 104. Sugar 400 

Importance 403 

§ 105. Accidental Abnormal Constituents 406 

Lead 407 

Copper 407 

Zinc 408 

Nickel and Cobalt 408 

Arsenic and Antimony 408 

Tannic Acid 408 

Alcohol, Carbolic Acid, and Chloroform 408 

Quinia 409 

IV. 

§ 106. Urinary Sediments. 409 

A. Non-Organized. 

§ 107. Uric Acid and Urates 410 

§ 108. Hippuric Acid 414 

§ 109. Earthy Phosphates 416 

§ 110. Oxalate of Lime. Calcic Oxalate 418 

Causes and Importance 419 

§ 111. Cystin 423 

§ 112. Xanthin— Hypoxanthin— Tyrosin 424 

B. Organized. 

§113. Mucus and Epithelium 425 

§ 114. Pus 428 

§ 115. Cancerous and Tuberculous Masses 430 



TABLE OF CONTENTS. 



XXI 



PAGE 

§ 116. Urinary Cylinders— Renal Casts 434 

1. Epithelial Casts 434 

2. Granular Casts 434 

3. Hyaline Casts 435 

Blood Corpuscles 437 

§ 117. Infusoria — Fungi — Kyesteine 437 

§ 118. Spermatozoa 440 

Entozoa 440 



DIVISION SECOND. 

§ 119. Quantitative Changes in the Urine. 443 

I. Quantitative Alterations of the Urine ivliich are easily Demonstrated. 444 

§ 120. Quantity of Urine 444 

Variation in Disease 451 

§ 121. Solid Residue and Specific Gravity 453 

§ 122. Quantity of Urinary Pigment 461 

§ 123. II. Quantitative Alterations of the Urine loMcli require a compli- 
cated Chemical Ancdysis for their Demonstration 465 

§ 124. General Rules for the Quantitative Analysis of Urine 467 

§ 125. Urea 473 

§ 126. Uric Acid 481 

§ 127. Free Acids 484 

§ 128. Ammonia 486 

§ 129. Chlorine and Chloride of Sodium 489 

§ 130. Sulphuric Acid 497 

§ 131. Phosphoric Acid , 504 

§ 132. Earthy Phosphates 511 

§ 133. Potassium 515 

Kreatinin 515 

Leucin and Tyrosin 516 

Allantoin 517 

Lactic and Oxymandel Acids. . . , 517 

Carbonic Acid 517 

§ 134. Concluding Observations 518 

(Illustrative Cases.) 

APPENDIX. 

§ 135. Introduction to the Examination of Urinary Calculi and other 

Urinary Concretions 531 

Description of the Plates 540 



INTRODUCTION. 



With the rapid development of chemistry in the last few 
decades, its reaction upon other arts and sciences has been 
manifest. Where do we find now a rational manufacturer or 
farmer who does not constantly appeal to chemistry, so much 
is he impressed with its importance ? Who can question the 
important services it has rendered medical science already? 
Physiology and pathology owe a great part of their rapid 
growth of late years to the development of this young science. 
How simple have the processes of respiration and nutrition 
become, since chemistry with balance and weights has deter- 
mined the metamorphosis ! Physiologists and physicians have 
long recognized the importance of the earnest study of this 
process, and have turned their attention to the investigation of 
the rapidity of the transformation of tissue. 

Zoochemical analysis, through the earnest zeal of so many 
observers, has naturally flourished and rapidly developed. It 
soon taught that the urine was the special storehouse for the 
decomposition products of animal tissues, and that its study 
would give conclusive information concerning the organic pro- 
cesses in the diseased as well as in the healthy body. This 
secretion has, therefore, been investigated with great diligence, 
since the first origin of zoochemical analysis. Many substances 
were discovered in it, and many appearances observed which 
permitted conclusions to be drawn concerning the function of 
the organism. 

Unfortunately, until within a short time, the analysis of the 
urine was a very protracted and laborious undertaking, and 
could not be performed by practising physicians. How different 
has this become in modern times ! It is now possible for medi- 
cal men, furnished with the simplest and most accurate methods, 

xxiii 



xxiv INTRODUCTION. 

to test tlie urine at tlie bedside in a sliort time, eitlier for tlie 
discovery of a few abnormal constituents, or for determining 
the quantity of several of the normal contituents. If, in addi- 
tion, the microscope be used rationally, all the conditions are 
given for an accurate determination of th6 changes in the organ- 
ism from the composition of the urine. 

In the following pages I shall first give a description of nor- 
mal urine, and at the same time call attention to the peculiar 
changes which it undergoes in the acid and alkaline fermen- 
tation. The chemical properties of the normal and abnormal, 
organic and inorganic constituents is added to the first part, in 
which I shall pay special attention to the appearances of each 
under the microscope. 

The second part treats exclusively of the different quantita- 
tive methods, with a detailed account of the necessary precau- 
tions, manipulations, and contingent modifications. 

The third part, on the other hand, contains a practical 
guide to the qualitative and quantitative examination of the 
urine and its sediments, in accordance with the present stand- 
point of chemistry. 

The following is a summary of the entire contents : 

I. Division. 

1. Physical and chemical properties of normal urine. 

2. Normal constituents. 
a. Organic. 

h. Inorganic. , 

3. Abnormal constituents. 

4. Sediments. 

5. Accidental constituents. 
II. Division. 

Quantitative estimation of the various organic and 
inorganic constituents. 
III. Division. j 

1. Practical guide to qualitative analysis. 

2. Eecognition of sediments under the microscope. 

3. Practical guide to quantitative analysis. 

4 Practical guide to the approximate quantitative esti- 
mation. 
Analytical notes. 



PART FIRST. 



A TREATISE 



CHEMICAL AND MICROSCOPICAL CHARACTERISTICS AND 
PROPERTIES OF THE URINARY CONSTITUENTS ; 

TOGETHER WITH A 

GUIDE TO THE QUALITATIVE AND QUANTITATIVE CHEMICAL 

EXAMINATION 

OF NOMAL AS WELL AS AB.NOMAL UKINE. 



GAEL NEUBAUEE. 



Analysis of the Urine. 



DIVISION FIEST. 

I. PHYSICAL AND CHEMICAL PROPERTIES OF NORMAL URINE. 



It is an established fact tliat the urine, physiologically con- 
sidered, is a true secretion by organs specially adapted for that 
purpose, the kidneys. We find in it, in the form of soluble 
nitrogenous and saline compounds, those elements which by 
transformation have become useless to the economy. 

Generally considered, the constituents of normal urine may 
be regarded principally as the products of metamorphosis of the 
animal tissues, etc. Most important are the organic nitroge- 
nous constituents of the urine : urea, uric acid, hippuric acid, 
oxaluric acid, kreatinin and xanthin, besides the coloring and 
extractive matters. Of these in human urine, urea occujoies 
the first place ; it is the most important product of retro- 
grade metamorphosis of the nitrogenous constituents of the 
body, from which it is formed by the oxidizing power of the 
organism in a manner yet unknown, since hitherto it has not 
been possible, in spite of many attempts, to produce urea arti- 
ficially by the action of energetic oxidizing agents ^ on protein 
substances. 

Indeed, several facts indicate that, in the oxidation of the 

■^ The repeated assertion of Bechamp that urea may be formed by the action 
of permanganate of sodium on protein bodies has not been confirmed by Stade- 
ler, Loew, and myself. 

3 



4 AliALYSIS OF THE UBINK 

different varieties of albumen, in the economy, its nitrogen is 
not directly converted into the form of urea, but previously 
a number of intermediate j^^oducts are formed, which, by 
further decomposition, furnish urea. Thus, O. Schultzen and 
Nencki ^ found that leucin and glycocoll, even when rapidly 
absorbed into the economy in large amounts, were eliminated 
in the form of urea ; and, according to the experiments of Von 
Knieriem,t ammonium chloride, asparagin, and asparagic acid, 
which latter was discovered by Eadziejewski and E. Salkowski 
to be the product of the digestion of fibrine by the pancreatic 
ferment, likewise cause an increase of urea in the urine. In 
the same way, in those diseases in which oxidation is much 
impaired, as acute yellow atrophy of the liver, etc., very large 
quantities of leucin and tyrosin are found in the urine, sub- 
stances which Kiihne showed were formed in large amount by 
the action of the pancreatic ferment on albuminates, while, in 
such cases, urea often wholly disappeared, and at the same 
time, paralactic acid, which, under normal conditions so readily 
oxidizes, was largely present.:]: 

Besides the above-named bodies, the mineral constituents of 
the blood, which have become physiologically useless, as well 
as many other substances entering into the economy, which 
are unnecessary for the process of metamorphosis, or are even 
injurious, are discharged with the urine, either unchanged or 
after chemical transformation. Finally, we must mention water, 
by the separation of which the kidneys regulate its amount in 
the blood, which is thus kept at a tolerably constant density. 
Normal urine, then, appears to be a very complex fluid, whose 
composition varies according to different classes of animals. 

Food exercises an undoubted influence on the composition 
of the urine, which is distinctly proved in the carnivora and 
herbivora. The urine of the former does not differ essentially 
from that of human beings. In the fresh state it is clear, 
light yellow, of unpleasant odor, bitter taste and acid reac- 
tion. The amount of urea is considerable, while the uric acid 
often entirely disappears, but soon increases, however, when 

* Berichte der dentsch. cliem. Gesellschaft, 1869, p. 566. 
f Zeitschrift ftir Biologie, Band 10, p. 263. 

X 0. Schultzen und L. Riess : Uber acute Phospliorvergiftung und Lebera- 
tropliie. 



PROPERTIES OF l^ORMAL TTRINE. 5 

tlie beasts are deprived of tlieir free exercise, as wlien confined 
in cages. 

Entirely different from this is tlie nrine of the herbivora, 
which is characterized by its constant turbidit}', alkaline reac- 
tion, and also by its considerable richness in carbonates of 
the alkalies and alkaline earths. It often contains a tolerable 
amount of urea, but is for the most -part rich in hippuric acid : 
uric acid is often wholly absent, and also the phosphates occur 
in very small amount. Calcic oxalate, together with crystal- 
lized calcic carbonate, is always found in the sediment of this 
urine. 

The influence of food on the composition of the urine appears 
most distinctly when herbivora are forced to digest only ani- 
mal food, or when they are made to fast for a long time, so that 
life is maintained entirely at the expense of the constituents of 
their own bodies. The urine thereby very soon loses its alka- 
line reaction, it becomes acid, urea appears in considerable 
quantity, the sediment of calcic carbonate disap|)ears, and uric 
acid in appreciable quantity is found. The urine, therefore, 
assumes the same character as that of the carnivora, a fact 
which can readily be demonstrated on rabbits.* Exactly the 
reverse occurs when carnivora are fed on a jDurely vegetable 
diet. 

The urine of birds, reptiles, etc., differs entirely from that of 
the mammalia, whence it must be inferred that the organiza- 
tion of these animals has a decided influence on the composition 
of the urine. 

Normal human urine shows, in general, more resemblance to 
that of the carnivora. Freshly passed it appears clear, of a light 
amber-yellow color, distinctly acid reaction, bitter, salty taste, 
and peculiar aromatic odor. Stadeler, in his great work, was the 
first to throw some light on the odorous matters in the urine, 
which work was chiefly on cow's urine, but included human 
urine also. By distillation of large quantities he succeeded in 
recognizing a series of peculiar volatile acids as the cause of 
the odor in cow's urine ; among these are to be mentioned car- 
bolic acid, also taurylic, damoluric, and damolic acids. Human 
urine contains very much smaller amounts of these acids, and 

* Annal. der Chemie und Pharm., Band 99, p. 106. 



6 ANALYSIS OF THE TTRINE. 

it is only hj taking very large quantities for examination that we 
can succeed in distinctly recognizing carbolic acid by its char- 
acteristic reactions. But whether these acids, and especially the 
carbolic acid, either free or combined with an alkali, are really 
constituents of normal urine, appears, from the more recent 
iuA^estigations of Buliginsky "^ more than doubtful, since these 
rather indicate that the carbolic acid is produced by the action 
of mineral acids on evaporated urine from a substance hitherto 
entirely unknown. 

The specific gravity of normal human urine varies according 
to age and sex, constitution of body, and food, and varies from 
1,005 to 1,030. 

There has been much dispute concerning the cause of the 
constant acid reaction of normal human urine, wdiich, accord- 
ing to the investigations of Kliipfel,t is considerably increased 
b}^ strenuous muscular exercise, while Sawicki % could not de- 
termine that rest or work had any influence on its acidity ; 
finally Liebig j^roved that the acidity arose chiefly from the acid 
phosphates. Since the experiments of Lehmann, there can be 
no doubt that in many cases free hippuric and lactic acids are 
found in the urine, which naturally contribute to the acid re- 
action. Under all circumstances the quantity as well as the 
quality of the food ingested has the greatest influence on the 
acidity of the urine. 

Since a solution of hyposulphite of sodium is immediately 
rendered turbid by a trace of free acid from the separated sul- 
phur, Huppert § made use of this salt with the best result to 
detect the presence of free acid, together with the acid salts, in 
a urine which has an acid reaction. Urea, which behaves like 
an ammonium compound with acids, and also, according to 
Lehmann's experiments, enters into fixed combinations with 
phosphoric acid, is, according to Huppert, not able to prevent 
the destructive action of acids on the hyposulphite of sodium, 
but only retards it. It is, therefore, to be considered that every 
urine, which, upon the addition of a solution of hy23osulphite of 
sodium, immediately becomes cloudy, contains free acids — free 

* Hoppe-Seyler, med. cliem. Untersucliung-en, Heft 2, p. 234. 
f Hoppe-Seyler, med. cliem. Untersuchungen, Heft 3, p. 412, 
X Pfliiger's Arcliiv, Band 5, p. 285. 
§ Arcliiv der Heilkunde, Baud 8, p. 354. 



PnOPERTIES OF NORMAL URINE. 7 

acids in tlie sense that tlie collectiye bases in tlic i:rine, urea, 
etc. included, are not sufficient to form witli tliem acid salts. 
If the separation of sulphur occurs only after a long time, 
there is, together with the ordinary acid salts, free acid present, 
which is in combination with urea. If, in urines which have 
an acid reaction, cloudiness does not occur at all on addition 
of the reagent, they contain only the ordinary acid salts. 
According to the investigations of O. Hammarsten ^ it appears, 
however, that variations in the amount of the hyposulphite of 
sodium added can change the results indefinitely, so that its 
value as a reagent for free acids and acid salts in the urine is 
somewhat doubtful. 

Urine can be kept for a long time in a closed vessel, pro- 
tected from contact wdth the air, without undergoing true de- 
composition. If we allow free access of air, however, it under- 
goes peculiar, not unimportant decompositions, which we will 
now consider more closely. If we leave fresh urine alone in an 
uncovered vessel, we perceive, in most cases very soon, the 
formation of light, small clouds of mucus, which gradually sink 
to the bottom, and in which we find with the aid of the micro- 
scope a few pavement epithelial cells from the bladder and 
urethra, as w^ell as a very few mucus corpuscles enclosed in a 
finely granular coagulum of mucus. We can also frequently 
readily see the separation of acid urates. On long standing, 
however, especially at a moderate temperature, the acid reac- 
tion frequently becomes stronger and distinct, and usually 
colored crystals of uric acid are deposited on the walls and 
bottom of the glass. It remains in this condition of increasing 
acidity for a few days at least, though it may last for two or 
even three weeks ; finally we notice that the acidity suddenly 
diminishes until it at last disappears entirely. The urine loses 
color, becomes lighter, and covered with a whitish iridescent 
pellicle, and gradually takes on an alkaline reaction, which is 
shown by an offensive ammoniacal odor. At this time the 
crystals of uric acid also disappear, and we see white granules 
and colorless, highly refractive, prismatic crystals of ammonio- 
magnesian phosphate. 

These changes are embraced under the names of the acid and 
alkaline fermentation of urine. 



* Jahresbericht fiir Tliierchemie, Band 4, p. 211. 



8 Al^ALYSIS OF THE URINE. 

Sclierer has furnished interesting explanations of this decom- 
position ; these are essentially as follows. He considers the 
primary cause of the acid fermentation of urine to be the vesi- 
cal mucus, which he regards as a ferment necessary to the de- 
composition of the extractive coloring matter ; the latter is de- 
composed by the mucus with the formation of lactic and acetic 
acids, so that an increase in the amount of the free acids is 
brought about. As an indication, and also, probably, as a 
cause of this act of fermentation, the urine now shows under 
the microscope considerable numbers of fermentation spores, 
which in appearance are very similar to those of yeast, only 
smaller, and which, like the latter, increase by budding, and 
are grouped together in rows. (Plate II., figs. 1, 2, and 4) By 
the formation of these strong acids the readily decomposable 
urates are broken up with the separation of uric acid, Avhich is 
then deposited in well-formed crystals. Almost always crys- 
tals of calcic oxalate are found in this sediment, concerning the 
formation of which I will speak more fully under sediments. 
(Plate IL, fig. 4.) 

If, after a longer or shorter time, the free acid begins to di- 
minish, then the second period of urinary fermentation, the 
alkaline, commences. Urea now suffers a decomposition, and 
becomes converted into carbonate of ammonium;"^ gradually 
the precipitated crystals of uric acid disappear, and whitish 
granules of urate of ammonium, and prismatic crystals of urate 
of sodium, which often cover the crystals of uric acid which are 
commencing to dissolve, appear instead. (Plate II., fig. 5.) As 
the decomposition increases and the alkaline reaction com- 
mences, a part of the ammonia combines with the phosphate of 
magnesium present in the urine, and very beautiful crystals of 
ammonio-magnesian phosphate, together with phosphate of 
calcium, separate in large amounts. (Plate II., figs. 3, 5.) This 
peculiar decomposition has the closest connection with the 
formation of sediments, and I shall return to it when I speak 
of them. 

* Together witL. carbonate of ammoniuin small amotints of other volatile 
bases, so-called substituted ammonias, appear to form also, of which Dessaignes 
has already observed trimethylamin, characterized by its odor of sea-fish, by the 
distillation of large amounts of human urine. (Annal. der Chemieund Pharm., 
Band 100, p. 128.) 



PROPERTIES OF NORMAL URINE. 9 

According to Voit and Hofmann ^' there is no acid fermenta- 
tion of urine, but only an alkaline one. The gradual separa- 
tion of amorphous and crystalline uric acid sediments they ex- 
plain .by the decomposing action which the acid phosphate of 
sodium exerts on the urate of sodium, whereby the acid reac- 
tion of the urine gradually diminishes, so that at no time can 
an increase in acid be proved. This in many cases is undoubt- 
edly correct, but not in all. As soon as yeast spores occur in a 
urine, and such cases are not rare, the increase of acid can be 
readily determined, most easily in very weak saccharine as well 
as in diabetic urines in which sediments of crystallized uric 
acid frequently and rapidly form, in spite of the fact that in 
pronounced cases of diabetes the other constituents of the 
urine, not excepting the acid phosphate of sodium, are very 
much diluted. As a product of this fermentation, acetic acid 
appears, which can be readily separated from every old urine, 
especially from old diabetic urine, in considerable quantity. 

According to the investigations of Schonbein, there is a fungus 
in every urine which forms gradually and undergoes fermenta- 
tion, and which in a short time changes pure urea into carbon- 
ate of ammonium. According to Pasteur and Tieghem, a torula 
is present which forms in the interior of the fluid, especially 
on the bottom of the glass, as a white deposit. Under the mi- 
croscope this shows rosary-like strings or clumps of small round 
globules with a diameter of 0'0015 millim., without granula- 
tions or recognizable sheath, and which seem to increase by a 
process of budding. 

Of all the substances which occur in human urine, without 
doubt urea is by far the most important, and as we have already 
seen above, is essentially the final product of the retrograde 
metamorphosis of tissue. Urea forms the middle step by which 
the nitrogen, which has become useless in the body, is given 
back to inorganic nature, since, when once removed from the 
body, it decomposes very easily, in contact with decomposing 
matter, into ammonia and carbonic acid, to begin the circle anew 
in this form as food for plants. Next to urea comes uric acid, 
which is also the result of the metamorphosis of the nitrogen- 
ous constituents of the body ; it stands a step higher than urea, 

" Zeitsclirift fur analyt. Chem., Band 7, p. 397. 



10 ANALYSIS OF THE URINE. 

and decomposes by continuous oxidation into urea and carbonic 
acid. Its amount is very much less than that of urea, and it is 
not in a free state like the urea, but is in combination with bases. 

Besides uric acid, we meet also in all urine with small 
amounts of hippuric acid, the origin of which is not yet precise- 
ly proved, although it is jDrobable that it is formed in a similar 
manner to urea and uric acid, and is an intermediate product in 
the process of retrograde metamorphosis. Besides these bodies, 
every urine contains, in addition, small amounts of xanthin, 
kreatinin, oxaluric acid, and coloring and extractive matters, 
about the chemical nature, origin, etc., of which but very little 
is yet positively known. Liebreich * claims to have found in 
urine a small amount of an organic base which has a resem- 
blance to neurin, obtained by him by the destruction of prota- 
gon by baryta water, and which possibly may be a product of 
the oxidation of the neurin. We also find of mineral constitu- 
ents, chlorides, chloride of sodium, chloride of potassium, and 
small amounts of chloride of ammonium, besides phosphates, 
especially acid phosphate of sodium and small quantities of 
magnesium and calcium phosphates and sulphates, traces of 
iron and silicic acid. Schunbein has also detected small quan- 
tities of nitrates, which in the alkaline fermentation of the urine 
are converted into nitrous acid, likewise traces of peroxide of 
hydrogen. A certain not altogether inconsiderable amount of 
carbonic acid from the blood, flowing through the urinary or- 
gans, gets into the urine and is eliminated with it. 

According to Bechamp, all normal urine contains also a pecu- 
liar ferment, nephrozymose, which, like the ferment of saliva, is 
capable of changing starch into sugar. Finally, that consti- 
tuent of the urine, which, under certain conditions, as I first 
discovered after the addition of a solution of chloride of zinc, 
shows a beautiful emerald-green fluorescence, has been recently 
more carefully investigated by Jaffe,t and since he found the 
same thing in bile, it has been named urobilin. 

Besides the hitherto mentioned organic and inorganic normal 
constituents of urine, there are the pathological and so-called 
accidental ones. The former are : albumen, sugar, biliary mat- 

^Bericht der deutschen cliem. Gesellscliaft, Band 2, p. 12. Cliem. Central- 
blatt, 1869, p. 12. 

f Zeitschrif t fiir analyt. Chem., Band 3, p. 346, und Band 9, p. 150. 



NORMAL CONSTITUENTS OF URINE, ORGANIC. H 

ters, fat, mucin, leucin, tyrosin, and several others wliicli are 
met with in the urine in certain disturbances of the health, 
while the latter, the accidental, may be of very different sorts, 
according as one or the other body is accidentally or intention- 
ally introduced into the economy, and is removed with this fluid, 
either unchanged or after previous chemical decomposition. 

We will now consider more particularly the different normal 
constituents, organic and inorganic, as well as the pathological 
and accidental ones. 



II. NORMAL CONSTITUENTS OF URINE. 

A. Organic. 

§ 2. Urea. 



Formula : CH.^.a hydrogen 6-67 
Nitrog-en 46-67 



Carbon 20-00 

Hydrogen 6-67 

Nitrogen 46-67 

Oxygen 26*66 



100-00 

A. Presence. Urea is found in the urine of mammalia, birds, 
and reptiles; it is most abundant in that of the carnivora. 
But, besides in the urine, we find it constantly in the blood, 
where it often is very considerably increased, especially in kid- 
ney diseases (Bright's disease), or after extirpation of the 
kidneys. This last circumstance indicates that urea is not 
formed in the kidneys, but in the blood, by an oxidation of 
nitrogenous matters which have become useless, fragments of 
tissue or superfluous nitrogenous bodies in the blood. 

In the muscular juice of men and sucking beasts, urea has 
hitherto not been detected, though other bodies have been 
found, as kreatin, xanthin, sarkin, etc., from which urea can be 
produced artificially. Whether the above bodies, among which 
also belongs the uric acid normally found in the blood, are the 
precursors of urea, and after further decomposition are excreted 
partly as urea, is not yet perfectly proved ; at least it appears 
from Voit's experiments^ that the kreatin of muscle takes no 

* Zeitsclirift fur Biologie, Band 4, p. 77, etc. 



12 ANALYSIS OF THE URINE. 

part in tlie formation of urea, and also tlie experiments oJ 
Ssubotin, according to whom nrea is formed from kreatin undei 
tlie influence of the renal tissue, have not been confirmed."^ On 
the other hand, it is an established fact that, after the intro- 
duction of uric acid, guanin, allantoin, thein, gluten, glycocoll, 
and leucin, also after partaking of food rich in nitrogen, an 
increase in the urea can readily be determined. t 

Moreover, the experiments of von Knieriem % showed that 
chloride of ammonium, asparagin, and asparagic acid increase 
the urea in urine, a fact which is the more interesting in that 
asparagic acid has been detected by Radziejewski and E. Sal- 
kowski§ among the products of the digestion of fibrine by 
means of pancreatic ferment. 

Besides in the urine, urea is found normally in the blood,|| 
bile, and liver, in the amniotic fluid, in the vitreous and aqueous 
humors, and finally, Funke and others have found it in the 
sweat. "Wurtz found it in the lymph and chyle of several ani- 
mals ; Lefort, in the milk of healthy cows. Urea appears to 
be wanting normally in the muscle of human beings and of 
most vertebrates. At least it has not been possible, thus far, to 
detect it in this tissue. It is probable, however, that urea 
occurs in the muscles and organs of many animals where it has 
hitherto not been found in mankind. Stadeler and Frerichs 
found considerable quantities of urea in the muscle and in 
almost all of the organs of many cartilaginous fishes (plagio- 
stomes), while they sought in vain for it in corresponding parts 
of the body of bony fishes. 

If the separation of urea by the kidneys is more or less im- 
peded, or even entirely suspended, we see it appear in almost 
all of the animal fluids. It first seems to be increased in the 
blood, and readily passes thence into the serous exudations ; 
under these circumstances urea has been found in the juice of 
muscle, in saliva, in the vomitus, and even in pus and milk. 
The sweat is then es]3ecially rich in urea, so that after its evap- 
oration a slight crust of urea remains. 

* R. Gsclieidlen's Habilitationssclirift, Leipzig, 1871. 

f Bericlit der deutscli. cliem. Gesellscliaft, 1869, p. 566. 

X Zeitschrift fiir Biologie, Band 10, p. 263. 

§ Berliner Bericlite, Band 7, p. 1050. 

II Annal. der Cliem. Pharm., Band 156, p. 88. 



NORMAL CONSTITUENTS OF URINE, ORGANIC. 13 

After tlie artificial introduction of urea into the body under 
normal circumstances it is not decomposed, but the economy 
frees itself very quickly from it, so that we may often, within a 
few minutes, detect a considerable increase of the urea in the 
urine. Gallois saw a rabbit weighing two kilograms die, after 
being given twenty grams of urea. First there occurred an in- 
crease of the respiration, then followed weakness of the limbs, 
trembling, general convulsions, tonic spasms, and finally death. 
The urine of a healthy individual contains, on an average, 
with a mixed diet, 2*5 to 3-2 per cent, of urea, so that within 
twenty-four hours between 22 and 35 grams are eliminated. 
The amount of urea excreted, however, is very variable, and 
depends very much on the weight of the body and on the food. 
Thus, Lehmann with a purely animal diet saw the twenty-four 
hours' amount of urea increase to 58 grams ; on a diet poor in 
nitrogen, on the contrary, it fell to less than fifteen grams, but 
with entire deprivation of food the urea did not ever wholly 
disappear. 

The artificial formation of urea can be brought about in very 
different ways. For example, cyanate of ammonium, which has 
the same elementary composition as urea, becomes urea imme- 
diately upon heating its solution. It can, moreover, be pro- 
duced from kreatin, guanin, allantoin, alloxan, oxamide, and 
many other bodies. Uric acid, by the action of strongly oxidiz- 
ing substances, produces as final products only urea, carbonic 
acid, and water. Nathansen obtained urea by heating carbonic 
ether with an excess of ammonia, and also by the action of 
chloro-carbonic oxide gas on dry ammonia gas. I can confirm 
both of these methods of formation. According to Basaroff it 
is also formed by prolonged heating of dry carbamate of ammo- 
nium, and also ordinary sesquicarbonate of ammonium, in sealed 
tubes, to 130° or 140" C. 

B. Preparation. 

1. From Urine. Two volumes of urine are treated with one 
volume of baryta solution, such as is used for the quantitative 
estimation of urea, the precipitate of phosphate and sulphate 
of barium is filtered off, and the filtrate evaporated to dryness 
on a water bath. The residue is extracted with alcohol, after 
filtering is again evaporated to dryness, and the mass which 
now remains is treated with absolute alcohol. The solution 



14 AJSTALYSIS OF THE URINE, 

contains pure urea wliicli after evaporation crystallizes in the 
form of colorless needles. Should the urea thus obtained not 
be perfectly colorless, it can be made so by treating it with a 
little pure animal charcoal. 

For the isolation at the same time of kreatinin, xanthin, and 
urea from one and the same specimen of urine, see below under 
Xanthin, § 5. 

2. From Cyanate of Ammonium. 80 grams of dried ferro- 
cyanide of potassium are melted by gentle heat with 30 of car- 
bonate of potassium, until a specimen removed solidifies to a 
milk-white glass. When this point is reached, the crucible is 
removed from the fire, and 150 grams of red oxide of lead are 
gradually added in small portions ; it is then heated about ten 
minutes, with frequent stirring, and the mass is poured on to an 
iron plate. After cooling, the raw cyanate of potassium is dis- 
solved in a solution of 80 grams of sulphate of ammonium in 
4 or 500 of water, filtered when all is dissolved, and the filtrate 
evaporated to dryness. The dried mass is extracted with small 
portions of alcohol (1-200 grams, 90 per cent), boiled several 
times, filtered, the alcohol distilled off again, and the mass 
allowed to crystallize. 

J. Williams recommends using commercial cyanide of potas- 
sium instead of the ferrocyanide. He extracts the fused mass 
oxidized by red oxide of lead with cold water ; after powdering 
it, frees the filtrate from the carbonates by the addition of 
nitrate of barium, and thus precipitates from the clear solution 
pure cyanate of lead by the addition of nitrate of lead, and de- 
composes the former, after washing and drying it, by digesting 
while hot with the equivalent amount of sulphate of ammonium, 
dissolved in the necessary amount of water. 

C. 3Iicrosco2nc Properties. If pure urea is crystallized quickly 
from a concentrated solution, it appears under the microscope 
in the form of white, silky, lustrous needles. If, however, we 
allow the crystallization to take place slowly from dilute solu- 
tions, it forms white, almost transparent, beautifully lustrous, 
striated, four-sided prisms, whose ends are terminated by one 
or two oblique surfaces. (Funke, Taf. IL, fig. 4; 2'^ Aufl. III., 
1.) These crystals belong to the rhombic system. 

D. Chemical Properties. Urea has a bitter, cooling, taste, simi- 
lar to that of saltpetre. Its crystals contain no water of crys- 



NOBMAL CONSTITUENTS OF URINE, OUGANIC. 15 

tallization, are permanent in the air, and readily dissolve in 
water and alcoliol. The solutions are neutral. It is almost 
insoluble in ether. 

1. Urea heated moderately on platinum foil melts with the 
evolution of ammonia; on being heated somewhat more it 
solidifies again, becomes brown, and finally burns readily and 
completely without leaving a residue of carbon. 

2. Urea heated with concentrated mineral acids, as sulphuric 
acid, etc., or with caustic potash or soda, undergoes decomposi- 
tion. One molecule of water is absorbed, and carbonic anhy- 
dride and ammonia are produced. (Quantitative estimation by 
the method of Ragsky and Heintz.) It undergoes this decom- 
position also when nitrogenous organic matters capable of 
decomposition (cause of the alkaline fermentation of urine) 
are added to its solution ; and second, when heated for a long 
time in a sealed tube with caustic baryta to a higher tem- 
perature than 100^. (Quantitative determination by Bunsen's 
method.) €H,N,a + H,0 = CO, + 2NH3. 

3. If nitrous acid or a solution of mercurous nitrite in nitric 
acid be added to a solution of urea, it decomposes into water, 
carbonic anhydride, nitrogen, and ammonia. (Liebig, Wuhler, 
Ludwig, and Krohmeyer.) 01I,]S^a4-IS^H05+NHa3=C02 + 2:N^ 
+ NH4,N03 + HoO. 1 gram of urea furnishes, therefore, 1*2 grams 
of escaping gas. 

According to the investigations of A. Claus,* the reaction 
takes place in the above-mentioned way only when the neces- 
sary amount of nitrous acid is added to the urea in the cold and 
then heated ; and second, when at the same time with the nitrous 
acid an equivalent amount of a stronger acid is added. In the 
last case it is immaterial whether heat is applied at first or 
later ; also the addition of an excess of nitrous acid is not im- 
portant. 

4. If a solution of urea is warmed with nitrate of silver, an 
insoluble precipitate of cyanate of silver is formed, and the 
solution contains nitrate of ammonium. In this way it can be 
converted into the same form of combination (cyanic acid and 
ammonia), from which it can be produced artificially. 

5. Mercuric oxide forms several stable compounds with urea, 

* Zeitsclirift fiir analyt. Cliemie, Band 10, p. 226. 



16 AJSTALTSIS OF THE URINE. 

in wliicli, according to circumstances, two, three, or four equiva- 
lents of mercuric oxide combine with one equivalent of urea. 

6. A solution of mercuric nitrate produces in a solution of 
urea a white flocculent precipitate, which, according to the con- 
centration of the fluid, has a variable composition. The pre- 
cipitate contains to one equivalent of nitrate of urea, two, three, 
or four equivalents of mercuric oxide. 

Corrosive sublimate, on the contrary, in a feebly acid solution 
of urea, gives no precipitate, but it does in an alkaline solution. 
On this the quantitative estimation of urea and chlorine by 
Liebig's method depends. 

7. Urea treated w^ith a solution of hypobromite or hypo- 
chlorite of sodium decomposes into nitrogen, carbonic acid, and 
water. The carbonic acid is rapidly absorbed by the lye, so 
that the urea can be determined quantitatively by direct meas- 
urement of the nitrogen.-^ GH,N,a+3:N'aCia=:3NaCl + Ca2 + 2H,a 
+2N. This method, on account of its rapidity, is to be highly 
recommended for clinical purposes. 

8. Urea in alkaline solution at ordinary temperature resists 
the oxidizing influence of permanganate of potassium very ener- 
getically; in a hydrochloric acid solution, however, it decom- 
poses with great readiness on being heated into carbonic acid 
and ammonia. By this behavior urea appears to be the last end 
product of the retrograde metamorphosis, since in alkaline solu- 
tion, as in normal blood, it cannot be further oxidized by ox- 
idizing agents, and is thus essentially distinguished from uric 
acid, kreatin, guanin, etc., which stand on a somewhat higher 
step. Urea comports itself quite as indifferently with ozone, 
while uric acid decomposes very energetically with the produc- 
tion of urea. But in the presence of alkalies urea is decom- 
posed by ozone into carbonic acid and ammonia. t 

9. Urea forms with many salts (corrosive sublimate, chloride 
of sodium, nitrate of calcium, chloride of calcium, etc.) crys- 
tallizable compounds ; it also forms with many acids, organic 
(succinic, tartaric, citric, and gallic acids) as well as inorganic, 
crystallizable salts, of which three, the nitrate, phosphate, and 
oxalate, are especially important. 

* Davy, Leconte, Hufner. Journ. fiir prak. Cliemie, 1871, p. 1. 

f Compare also Cliapman and Smitli in tlie Chem. Centralblatt, 1868, No. 308. 



NORMAL CONSTITUENTS OF URINE, ORGANIC. 17 

a. Nitrate of Urea. GH,N^,a,NHQ3.— (C2H,N,02,N05HO). If tol- 
erably concentrated pure nitric acid, free from nitrous acid, is 
added to a concentrated solution of urea, tliis compound sepa- 
rates, after tlie mixture becomes cool, in white shining plates 
or scales, which are mostly single, but often in superimposed 
masses. 

If only a small amount of urea is present, the compound is 
allowed to form under the microscope, best in the following 
way : The end of a little piece of thread is laid in the drop of 
fluid to be tested for urea, a covering glass is placed over the 
drop and one-half of the thread, while the other end of the 
thread is moistened with a drop of pure nitric acid. The two 
fluids gradually mingle, and the crystals form under the cover- 
ing glass on both sides of the thread with great regularity. If 
the crystals are watched during their formation we find, first, 
together with many complicated forms, rhombic tables or short 
prisms, whose acute angle measures 82°. The forms are changed 
by modification of the obtuse angle by faces into hexagonal 
tables or six-sided prisms. Such a regular development, how- 
ever, only occurs during slow crystallization, while, when the 
crystals form rapidly, a large number of six-sided tables overlap 
each other like tiles on a roof. Frequently, also, obtuse rhom- 
bic octahedra of little durability form at the first meeting of the 
two fluids, their acute angle measures 82°, but a greater num- 
ber of particles always accumulate on these, so that the primi- 
tive octahedra are changed into the above-named rhombic or 
hexagonal tables. Finally, very characteristic twin crystals are 
observed Avhich, with mutually oblique end-surfaces, are formed 
by the turning of one crystal 180°, corresponding to the well- 
known forms of gypsum. (Plate II., fig. 6.) 

This salt, which is permanent in the air, is readily soluble in 
water, more difficultly soluble in water containing nitric acid, 
and most difficultly soluble in alcohol containing nitric acid. 

Heated quickly on platinum foil it deflagrates, but at 140^ 
decomposes into carbonic acid, nitrous oxide, urea, and nitrate 
of ammonium. 

On mixing a concentrated solution of nitrate of urea with 
oxalic acid, the second compound oxalate of urea is precipi- 
tated. 

b. Oxalate of Urea. (€H,N,0)„€,HA + H,0.— [(OAN.O,). 

2 



18 AlfALTSIS OF THE UHINE. 

C4H0O8 + 2HO.] This compound also forms on mixing oxalic 
acid with a concentrated solution of urea ; it is precipitated in 
long, thin laminae or in prisms. If the formation is allowed 
to take place under the microscope, it usually appears similar 
to that of nitrate of urea in hexagonal tables; at times, how- 
ever, also in forms of four-sided prisms. (Funke, T^f. II., fig. 
6 ; 2'^ Aufl., III., 3.) 

This compound is readily soluble in water, but is precipitated, 
again from the solution by an excess of oxalic acid. On be- 
ing heated it decomposes into carbonate of ammonium and 
cyanuric acid. 

c. Pliosphate of Urea, ^H.^APH^O,— [0,H4]Sr,023HO,PO,], was 
obtained by Lehmann from the evaporated urine of pigs fed on 
bran, but it can also be artificially produced in large glisten- 
ing crystals, belonging to the rhombic system, by phosphoric 
acid and urea. The crystals are very easily soluble in water, 
and do not decompose in the air. 

E. Detection. In order to detect urea in the urine it is suffi- 
cient, in most cases, to evaporate a small quantity, 15 to 20 
grams, to a syrupy consistence on a water bath, and to treat 
the residue repeatedly with alcohol until a drop evaporated on a 
w^atch glass does not leave any residue. The urea is contained 
in the alcoholic solution, and remains behind more or less 
colored after the alcohol is expelled by evajDoration on a water 
bath. Dissolved in a little water, and a part treated with pure 
nitric acid, and a part with a concentrated solution of oxalic 
acid, it furnishes the two above-named compounds. If very 
small quantities are allowed to cr3^stallize with nitric acid 
under the microscope, the crystalline forms mentioned above, 
under nitrate of urea, will be seen to form. If, however, the 
urine contains albumen, the above portion is treated with a 
drop of acetic acid, heated to boiling, so that the albumen is 
entirely coagulated, filtered, and the filtrate treated as before, 
first evaporated on the water bath, then the residue extracted 
with alcohol, etc. 



J^OniTAL CONSTITUENTS OF URINE, ORGANIC. 19 



§ 3. Kkeatikii^. 



Formula: €4H:N3a 

[CeH,X30j 



^Carbon 42-48 

Hydrogen 6-19 

Nitrogen 37-17 

.Oxygen 14-16 



100-00 



A. Presence. Kreatinin, by all means tlie strongest base of the 
animal body, was first discovered by Liebig in the crystalline 
precipitate which Heintz, and later Pettenkofer, obtained from 
concentrated urine with a solution of chloride of zinc. Liebio- 
found in this chloride of zinc compound, kreatinin together with 
kreatin, and therefore arrived at the conclusion that both 
bodies were originally contained in the urine. But Heintz 
furnished proof later, by a very thorough investigation, that no 
kreatin is contained in fresh urine, but that it is formed by the 
decomposition of the chloride of zinc compound of kreatinin by 
the absorption of water by the kreatinin, a fact which has now 
been confirmed by Liebig and Dessaignes. Since kreatin can 
readily be changed into kreatinin by withdrawing water, the 
kreatin, which is always to be found in the juice of muscles, be- 
comes in the blood, or, according to Yoit, more probably in the 
kidneys, kreatinin through loss of water, and is then discharged 
in this form with the urine. Dessaignes, on the contrary, thinks 
that the fluid of muscle, like the urine, originally contains only 
kreatinin vdiicli first becomes kreatin by the separation of 
water caused by the long-continued action of warmth in the 
neutral fluid. But according to my investigations the matter 
is just the opposite. By the method described under kreatin 
this body can be obtained pure in a very short time from the 
juice of muscles ; and I have also proved with certainty that 
kreatin, by long heating in a watery solution, gradually be- 
comes converted into kreatinin. In the juice of muscles there 
is no kreatinin, but only kreatin, and when the former is found 
it has been formed from kreatin by the too long action of heat. 
According to my own determinations there are from 0'6 to 1-3 
grams of kreatinin eliminated by a healthy man on good mixed 
diet in an average amount of 1,500 to 1,600 cubic centimeters 



20 ANALYSIS OF THE URINE. 

of urine in the twenty-four hours. Munk found an increased 
excretion of kreatinin in acute diseases, especially in pneumo- 
nia, typhoid fever at the height of the disease, intermittent 
fever, etc. A diminution occurred during convalescence from 
acute diseases, especially when the patients were very ansemic. 

Hofmann''^ found in his extended observations on himself 
a daily excretion of kreatinin of from 0*52 to 0'81 grm., the 
average was 0*681 grm. ; in others, on the contrary, the average 
was 0*99 grm. The urine of sucklings was found free from 
kreatinin ; it appeared first after partaking of meat. Boys ten 
to twelve years old passed a daily average of 0*387 grm. ; a 
person seventy years old, on the contrary, 0*517 to 0*593 grm. 
In women somewhat less kreatinin, on an average, was found 
than in men, the average of seven estimations was 0*65 grm. 
Physical exercise appeared to be Avithout influence ; meat diet 
considerably increased the amount of kreatinin in the urine, 
even in young children. Hofmann found a diminution of the 
excretion of kreatinin in cases of debility, deficient nutrition, 
and in diabetes. In advanced degeneration of the kidneys, in 
spite of an abundant meat diet, the excretion is diminished, 
which confirms the opinion of Yoit t that the transformation of 
muscle kreatin does not take place in the blood first, but in 
the kidneys, where the acid urine is separated from the alkaline 
blood. 

Besides in human urine Yerdeil and Marcet found it in the 
blood, Socoloff in the urine of the horse and sucking calves, 
Dessaignes in the urine of the cow, and Liebig in the urine of 
the dog. According to Scherer it ajDpears to be found also in 
the amniotic fluid. Voit obtained kreatin from the blood of 
calves, oxen, and sheep, but no kreatinin. 

B. Microscopic Projjerties. Kreatinin appears in the form of 
colorless, very glistening prisms, which belong to the monoclinic 
system. (Funke, Taf. III., fig. 2 ; 2'« Aufl., YL, 5.) 

C. Chemical Properties. Kreatinin is probably the strongest 
organic base of the animal kingdom ; it has almost as caustic a 
taste as ammonia, and is soluble in eleven parts of water at 12^ 
to 20^ ; it is more easily soluble in hot water. One hundred 

* Vircliow's Arcliiv, Band 48, p. 358. 

f Zeitsclirif t fiir Biologie, Band 4, p. 114 



NORMAL CONSTITUENTS OF URINE, ORGANIC. 21 

parts of cold alcohol dissolve about one part of kreatinin ; iu 
hot alcohol it is soluble in such amount, that it separates again 
on cooling in white crystalline masses ; ether takes up only a 
very small quantity. The solutions have a strongly alkaline 
reaction and caustic taste, like dilute ammonia. 

Kreatinin comports itself like a nitrile base; it directly com- 
bines with ethyl iodide, forming kreatinin ethyl iodide, from 
which ethylkreatinin is separated as a strong base by oxide of 
silver, and appears in a crystalline form. 

1. If a concentrated solution of chloride of zinc is added to 
a solution of kreatinin, a crystalline precipitate of kreatinin 
chloride of zinc immediately forms (Q^.-J^J^)JLTiC\o — [CgH^NyO., 
ZnCl]. The crystals are distinctly prismatic when formed very 
slowly ; on more rapid formation, however, only fine needles 
are seen under the microscope, which, grouped concentrically, 
either form complete rosettes or tufts, which cross each other, 
or of which two are so laid together with a short pedicle that 
they resemble pencils running into each other. Kreatinin 
chloride of zinc is difficultly soluble in cold water, more readily 
in hot water, but insoluble in alcohol. 

If kreatinin is separated from an aqueous extract of urine by 
chloride of zinc, the compound is obtained chiefly in the form 
of dark warty masses, in which, even under the microscope, a 
crystalline structure can scarcely be recognized. At times 
even here, distinct crystals in the form of a rosette, fine nee- 
dles, are obtained, which are united into broom and star-shaped 
masses. Kreatinin chloride of zinc is obtained from an alco- 
holic extract of urine by precipitating with an alcoholic solu- 
tion of chloride of zinc, always as a faint yellow powder, which 
under the microscope shows almost exclusively yellow, trans- 
parent, sharply defined spheres of different size, in which, with 
a high power (400), a striation may be distinctly seen. By 
dissolving this powder in hot water, regular forms can readily 
be obtained under the microscope. When the solution has 
completely cooled, a drop is placed on an object glass, and a 
little solution of chloride of zinc is added with the aid of a small 
piece of thread, just as was described under nitrate of urea, page 
17. Very soon the above-described characteristic rosettes of 
crystals, often of considerable size, are seen to form on both 
sides of the thread. 



22 ANALYSIS OF THE UPJNE. 

2. A not too dilute solution of kreatinin treated with a con- 
centrated solution of nitrate of silver, solidifies to a network of 
crystalline needles, wliicli dissolve in boiling water, but sepa- 
rate again on cooling. 

3. Mercuric chloride acts in a similar way. The precipitate 
is at first caseous, but changes in a few minutes to a mass of 
fine colorless needles. 

4. A solution of mercuric nitrate does not cause a precipi- 
tate immediately in dilute solutions of kreatinin, but if a solu- 
tion of carbonate of sodium is added to the mixture drop by 
drop till the turbidity remains j)ernianent, the compound crys- 
tallizes in beautiful microscopic crystals. In concentrated 
solutions the j)i'ecipitate forms very quickly, and if no free 
nitric acid is present, without the addition of sodic car- 
bonate. 

5. If an ammonium salt is heated with kreatinin, ammonia 
is evolved. 

6. Kreatinin gives with hydrochloric, nitric, and sulphuric 
acids, good crystallizable compounds, soluble in water : 

a. Chloride of kreatinin crystallizes in transparent prisms 
and broad leaves. With chloride of platinum it gives a com- 
pound similar to those formed with potassium and ammonium 
chlorides, which is easily soluble, and crystallizes in aurora- 
colored j^risms. 

b. Sulphate of kreatinin forms concentrically grouped, trans- 
parent, quadrilateral tables. 

It is to be emphatically remarked that kreatinin chloride of 
zinc, the most important compound of kreatinin, is not precipi- 
tated from chloride of kreatinin, etc., by the addition of a 
chloride of zinc solution. The separation follows immediately, 
however, if before the addition of the chloride of zinc solution, 
acetate of sodium in sufficient amount is added to the krea- 
tinin salt. 

7. By the action of mercuric oxide, lead peroxide, and sul- 
phuric acid, or permanganate of potassium, kreatinin, like krea- 
tin, is decomposed into oxalic acid and oxalate of methyluramin, 

G,H,]sr3a+ao + H.a == g„h,n,+GoHoO— [c^H^NaO^ + 40=c,h,n"3 
+ CA]. 

8. Kreatinin is formed from kreatin by the action of the 
mineral acids, or by the prolonged heating of an aqueous 



NORMAL CONSTITUENTS OF URINE, ORGANIC. 23 

solution to 100° C, wliile tlie latter loses two molecules of 
water. If a solution of kreatinin is allowed to stand a long- 
time in contact with alkalies, it becomes kreatin again by ab- 
sorbing water. Warmth favors the transformation. (Liebig, 
Dessaignes.) 

9. On heating with caustic baryta in an aqueous solution, 
kreatinin furnishes methylhydantoin with disengagement of 
ammonia. At the same time a syrupy acid is formed wdiich 
has not been closely examined. 

(Kreatinin) (Metliylhydantoin) 

When similarly treated, kreatin forms methylhydantoin to- 
gether with sarkosin and urea. (See Kreatin.) 

Methylhydantoin is formed artificially by melting together 
sarkosin an^ urea. (Huppert.)"^ 

10. Phosphomolybdic acid gives in aqueous solutions of pure 
kreatinin acidulated with dilute nitric acid a yellow crystalline 
precipitate, which forms immediately when diluted one thou- 
sand times, but only after prolonged standing when diluted from 
five to ten thousand times. In a great excess of hot nitric acid 
the compound dissolves, but on cooling it separates in beauti- 
ful very characteristic crystals, wdiose microscopic appearances 
are not without value in the detection and recognition of krea- 
tinin. (Kerner.) 

D. Preparation of Chloride of Kreatinin from Urine. Eight to 
ten liters of urine are evaporated to a third or quarter, and 
separated after cooling from the precipitated salts. The mother 
liquor is precipitated with a solution of sugar of lead, the excess 
of oxide of lead is removed by sulphuretted hydrogen, and a 
concentrated solution of corrosive sublimate is added to the 
filtrate, which is nearly neutralized with sodic hydrate. The 
precipitate, principally a compound of kreatinin with mercuric 
chloride, is suspended in water and decomposed with sulphu- 
retted hydrogen, the filtrate decolorized with animal charcoal 
and evaporated to crystallization. By repeated crystallization 

*Bericlit, der deutsclien clieni. Gesellscliaft, Band 6, p. 1378. 



24 AJVALY8IS OF THE URINE. 

from strong alcohol, wliite crystalline crusts are finally obtained, 
or large, hard, shining prisms of chloride of kreatinin. The re- 
moval of hydrochloric acid is accomplished by plumbic hydrate, 
as is shown below. (Maly.) 

E. Detection. Since kreatinin occurs only in small amount in 
the urine, large quantities are necessary for its certain recogni- 
tion, yet 2 to 300 cubic centimeters are sufficient for its qualita- 
tive detection in most cases. The process is as follows : The fresh 
urine is neutralized with milk of lime and the phosphoric acid 
precipitated by a solution of chloride of calcium. The precipi- 
tate is filtered off, and the filtrate eva23orated rapidly on a water 
bath to a thick syrup. The residue thus obtained is extracted 
with strong alcohol, best with absolute alcohol, allowed to stand 
a few hours, filtered, and the clear fluid treated with a concen- 
trated solution of chloride of zinc free from acid. After violent 
agitation a turbidity will soon appear, and after forty-eight 
hours the separation of the kreatinin chloride of zinc is com- 
plete. The compound is washed on a filter with alcohol, dried, 
and, according to C. 1, subjected to a microscopic examination. 
If we wish to 23roduce pure kreatinin, the compound which has 
been obtained is dissolved in a little hot water, and oxide of 
zinc and hydrochloric acid separated by freshly precipitated 
thoroughly washed, plumbic hydrate, with which the fluid is to 
be boiled at least a quarter of an hour. The fluid obtained by 
filtration is decolorized by boiling with animal charcoal, and is 
then evaporated to dryness. The residue, which is always a 
mixture of kreatinin and kreatin, is treated Avitli cold strong 
alcohol, by which the kreatinin is removed while the kreatin 
remains behind. By evaj)oration of the alcoholic solution 
kreatinin is obtained in pure crystals, while the kreatin is 
obtained readily in pure form by re crystallization from a little 
hot water of the residue insoluble in alcohol. It is to be 
observed that, when the solution of kreatinin chloride of zinc 
has been treated for a long time with oxide of lead, often only 
kreatin and no kreatinin at all is found in the residue. The 
latter becomes converted into kreatin by the prolonged action 
of the excess of oxide of lead by absorbing two molecules of 
water. 

If the urine contains albumen, it must first be separated by 
coagulation. In diabetic urine it is best, according to Gaeht- 



NORMAL CONSTITUENTS OF URINE, ORGANIC. 25 

gens," to first destroy the sugar present by fermentation with 
yeast. 

Kreatinin thus obtained is characterized by its strong basic 
qualities, by its tendency to form double compounds with the 
metallic salts, and salts with acids, as well as by its characteris- 
tic beha^dor with phosphomolybdic acid. It is distinguished 
from kreatin further b}^ its much greater solubility in strong- 
alcohol, as well as by its form of crystallization. 

Kreatin is not so w^ell characterized ; there is nothing better 
for its certain recognition than a comparison with the pure 
crystalline substance. 

The alcoholic extract of urine, from which, after acidifying 
Tvith hydrochloric acid, hippuric acid has been separated by 
shaking with ether, § 8, E. 2, is best used for the detection of 
kreatinin. After the ether is removed, the hydrochloric acid is 
accurately neutralized with sodium hydrate, diluted with thirty 
to forty cubic centimeters of absolute alcohol, and the kreatinin 
precipitated by the chloride of zinc solution. 

According to Kerner, kreatinin may easily be detected by 
the following method : The urine is precipitated with a concen- 
centrated solution of mercurous nitrate, filtered, treated with 
sulphuretted hydrogen which is separated from the filtrate by 
warming and the addition of a drop of nitric acid, and while it 
is still warm is treated with phosphomolybdic acid. After 
cooling and standing a short time the phosphomolybdate of 
kreatinin separates in characteristic crystals, especially on the 
walls of the vessel, where they have been rubbed with a glass 
rod. (See above under C. 10.) 



§4. Kkeatin-. 






r Carbon 


36-64 


Formula: €4110^300 +Hoa 


Hydrogen 


6-87 


[0311,^304 + 2H0] ' 


Nitrogen 


32-06 


' 


L Oxygen 


24-43 



(Anhydrous.) 100-00 

A. Presence. Kreatin is found in the juice of striated, and 
also of smooth muscular fibre, according to my investigations, 

* Zeitschrif t fiir analyt. Cliem., Band 8, p. 100. 



26 aj^alysis of the urine. 

on an average of 0*2 per. cent. It lias, moreover, been found in 
greater or less quantity in the various transudations, in the 
blood, tlie brain, tlie kidneys, and tlie amniotic fluid. (See re- 
marks under kreatinin concerning its presence in tlie urine.) 

Not much can be said definitely about the physiological sig- 
nificance of kreatin. If we regard only its occurrence in the 
juice of muscle as well as its considerable richness in nitrogen, 
we would be inclined to regard kreatin as an im23ortant nutritive 
material ; but the ready decomjDosition of this body into urea, 
kreatinin, and sarkosin, which are without doubt to be regarded 
as excretive materials, stamp it rather as an excretive material, 
which stands on the ladder of retrograde metamorphosis as a 
middle step between those substances of the most complex 
(protein substances) and those of the simplest molecular com- 
position (urea, etc.). At all events, kreatin stands nearer to 
urea than to the protein substances. 

B. Preparation. Fresh, finelj^-chopped beef is thoroughly 
mixed with an equal amount of water, and the mass heated ten' 
or fifteen minutes on a water bath with constant stirring to 
55°-60° C, so that the albumen just commences to coagulate. 
It should then be strained through cloth, the residue squeezed 
out, and the fluid thus obtained heated to boiling to completely 
coagulate the albumen. After cooling it is filtered, and the 
filtrate treated with basic acetate of lead in slight excess. The 
lead precipitate is collected on a filter, w^ashed, and the excess 
of lead precipitated from the entire filtrate by sulphuretted 
hydrogen. After filtration from the sulphide of lead, a color- 
less filtrate is obtained, from which, after sufficient concentra- 
tion on the water bath, colorless kreatin crystallizes out after 
standing awhile. The crystals are to be collected on a filter, 
washed with alcohol, and dried in the air. After one recrystal- 
lization they are obtained absolutely pure. 

Kreatin may be obtained artificial^, by warming an alcoholic 
solution of sarkosin and freshly prepared cyanamid for several 
hours to 100° C. on the water bath." 

For its j)reparation from urine, see kreatinin under " Detec- 
tion." 

C. 3Iic7'oscopic Properties. Kreatin, when pure, forms colorless, 

-:^ Volhard, Cliem. Centralblatt, 1809, p. 3G4. 



JVOBMAL COIiSTITUENTS OF UlilSB, ORGAmC. 27 

perfectly transparent, strongly refractive prisms wliicli belong- 
to the monoclinic system. (Funlie, Taf. III., fig. 1 ; 2'" Anfl., 
Taf. IV., fig. 4.) In most cases it forms groups whose appear- 
ance reminds one of tliat of sugar of lead. 

If a dilute solution of kreatin is placed in a concave polished 
object glass and allowed to evaporate spontaneously, at first on 
the edge, a collection of long j)rismatic crystals is observed 
which are thick at their free ends and gradually become nar- 
rower. In the middle of the fluid regular crystals gradually 
form, principally prisms, which are often united by their acute 
angles in a fan shape. Single crystals have, in the middle, a 
characteristic bulging like those of lactate of zinc, narrowing 
toward the ends, and are terminated by two surfaces. Finally 
also, thick, apparently rectangular, tables, at times single, at 
times in large numbers, frequently appear. 

D. Chemical Properties. Kreatin has a bitter, harsh taste, dis- 
solves in seventy-five parts of cold water, and much more readily 
in hot water ; the kreatin separates from the solution again on 
cooling, as crystals, in the form of fine shining needles. It is 
with difficulty soluble in alcohol, one part requiring nine thou- 
sand four hundred and ten parts ; while ether does not dissolve 
any. 

1. The aqueous solution is without reaction on vegetable 
coloring matters, has a bitter taste, and very readily decom- 
poses. If a dilute solution of kreatin is evaporated slowly on 
the water bath, it gradually becomes converted into kreatinin. 
Dessaignes has recently succeeded in producing crystallizable 
salts of kreatin with sulphuric, hydrochloric, and nitric acids. 

2. If kreatin is boiled a long time with caustic baryta it de- 
composes into urea, sarkosin, and methylhydantoin. 

G.Ho^aO^ + H,a = OH,^T.^o + GaH.isra^ 

[CSH3N3O4 + 2H0 = O2H4N2O2 + C,H,N O4] 

(Kreatin) (Urea) (Sarkosin). 

[CsH,N304-NH3=CsHeN,OJ 

(Kreatin) (Methylliydantoin). 

If the action continues too long, the urea splits up into car- 
bonic acid and ammonia ; the latter escapes while the carbonic 
acid combines with the barium. Sarkosin can be obtained in 



28 AJ^ALYSIS OF TUB URINE. 

colorless crystals, tliougli with difficulty ; metliylliydantoin crys- 
tallizes more easily, and can be separated from the sulphate of 
sarkosin by treating with alcohol. 

3. Dilute mineral acids dissolve kreatin without decomposi- 
tion, but boiled with concentrated acids it changes into kreatinin 
by giving up water. 

(Kreatin) (Kreatinin). 

4. Pure kreatin in dilute solution is not precipitated by chlo- 
ride of zinc. From a concentrated solution kreatin chloride of 
zinc crystallizes in hard crystals. Similar compounds are fur- 
nished by kreatin with chloride of cadmium, chloride of copper, 
and mercuric nitrate. 

5. Peroxide of lead has no action on kreatin; it is, on the 
contrary, decomposed by permanganate of potassium ; the de- 
composition j)roducts which are formed, with the exception of 
carbonic acid, are unknown. Perhaps urea is one of them. 

6. A solution of kreatin, boiled Avith an excess of mercuric 
oxide, causes metallic mercury to be separated with evolution 
of carbonic anhydride, and the solution contains the oxalate of 
another powerful base, methyluramin (€0117^3). (See § 3, C. 7.) 

E. Detection. See Kreatinin. 

§ 5. Xanthin. 

r Carbon 39*5 

Formula: GsH.N.O, i Hydrogen 2-G 

[CioH^N.O,] ] Nitrogen 36-8 

[Oxygen 21-1 



100-0 



A. Presence. Xanthin was recognized by Scherer and Stadeler 
as a substance very widely distributed in the animal economy, 
while, until within a short time, it was known only as a very rare 
constituent of some vesical calculi. Scherer found xanthin in 
human urine, in the spleen, pancreas, brain, liver of the ox, in 
the thymus gland of the calf, and in the muscular tissue of the 
horse, ox, and fish, also in the spleen in cases of splenic tumor, 



NOBMAL CONSTITUENTS OF UBINE, OBGANIC. 29 

as well as in tlie liver in acute yellow atropliy. Mosler - found 
xantliin in tlie blood and urine in leukaemia, Dilrr and Stro- 
mejer found it in tlie urine after tlie use of sulpliur batlis. 
Bence Jones observed it once in a ten-year-old cliild as a uri- 
nary sediment. Xantliin w^as mostly accompanied by liypoxan- 
tliin; but in tlie spleen, liver, and brain by uric acid also. 
Salkowsky t i)roved tlie presence together with xantliin of a 
hypoxanthin-like body in very small amount in normal as well 
as in leukgemic urine. 

B. llicroscopic Properties. Xanthin is amorphous, and shows 
under the microscope no crystalline structure. A hot aqueous 
solution of xantliin deposits it on cooling, mostly in the form of 
colorless flocculi, at times, also, as a fine powder, which under 
the microscope appears to consist of round bodies which, when 
in the flocculent form, are arranged in rows, and in the powdered 
lie singly. 

C. Chemical Properties. Xanthin forms hard, white pieces, 
which on rubbing with the nail assume a waxy lustre. It is 
difficultly soluble in cold water, and somewhat more soluble 
in boiling water. It has been produced artificially from guanin. 

1. Ammonic and potassic hydrates, hydrochloric, nitric, and 
sulphuric acids dissolve xanthin. It is precipitated from its 
alkaline solutions by the addition of an acid, while it gives crys- 
talline compounds with the acids. 

2. The cold saturated aqueous solution gives with corrosive 
sublimate a white preci23itate ; when diluted thirty thousand 
times an evident cloudiness occurs, but Avhen diluted forty 
thousand times it is not perceptible ; with cupric acetate yellow- 
ish-green flocculi separate on boiling. The solution in ammo- 
nia is precipitated by chloride of cadmium and chloride of zinc, 
also by plumbic acetate ; the latter precijDitate often changes, on 
standing, into shining scales. 

3. Nitrate of silver causes in a nitric acid solution of xanthin 
a flocculent precipitate, which dissolves on heating and slowly 
separates again on cooling. Under the microscojDe the silver com- 
pound shows after rapid cooling hairlike, crystalline needles, but 
on slow cooling wavy aggregations of fine crystals are formed. 

* Hosier declares lie found sarkin (liypoxautliin), but tlie reactions described 
by liim correspond rather to tliose of xanthin than sarkin. 
f Vircbow's Arcbiv, Band 50. 



30 AJSTALYSIS OF THE URINE. 

In an ammoniacal solution of xanthin, nitrate of silver gives a 
gelatinous precipitate insoluble in ammonia. €5H4N40i, + Agoy. 
-[C,oH,NA + 3AgO]. 

4. Xantliin dissolves in nitric acid on heating without evolu- 
tion of gas, and a yellow residue remains after evaporating the 
solution, which residue does not become purple by the action 
of ammonia, but becomes yellowish red by adding potassic hy- 
drate, and when heated beautiful violet red. 

If uric acid is mixed with xanthin, as is the case in certain 
calculi which contain it, the above reaction is modified by the 
murexid reaction which takes place at the same time. This is 
the reason, according to Lebon,"^ Avhy xanthin has been so sel- 
dom found in calculi. To separate the two the powdered cal- 
culus is to be treated with hydrochloric acid and heated. 
Since uric acid is insoluble in hydrochloric acid, the filtrate 
contains only chloride of xanthin, which can be obtained by 
evaporation and used for the above reaction. 

5. If xanthin is dissolved in strono- hot hydrochloric acid 
beautiful microscopic crystals of chloride of xanthin separate 
on slow cooling in the form of six-sixed tables, lying together in 
groups and rosettes. Very frequently, however, only spherical 
and oval forms can be seen. The nitric acid salt crystallizes in 
a similar form though not so characteristic ; here also rosettes 
are seen to form from rhombic tables and prisms. 

6. If calcic hypochlorite is mixed in a watch glass with sodic 
hydrate, and a little xanthin added, a dark green border first 
forms around the granule and soon becomes brown and finally 
disappears. (Hoppe-Seyler.) 

7. Phosphomolybdic acid produces, even in very dilute solu- 
tions of xanthin, a copious yellow precipitate. In hot dilute ni- 
tric acid this compound is soluble, but it separates, after cooling 
again, in regular microscopic cubes. (Scherer, Kerner.) 

8. Xanthin occupies the middle step between sarkin (hypo- 
xanthin) and uric acid. 

Sarkin GJI.N.O [0,0X14^40,] 
Xanthin 0,114^,02 [C10H4X4O4] 
Uric acid CJI4K4O3 [C,oH4lSr40J. 

* Comptes rendus, Bd. 73, p. 47. 



NOBMAL COIs'STITUEKTS OF URINE, OBGAWIC. SI 

T>. Detection. I give below a method wliicli not only insures 
tlie detection of xantliin in nrine, but^lso at the same time en- 
ables us to obtain kreatinin and considerable amounts of chemi- 
cally pure urea in one and the same j)ortion of urine. 

1. Xantliin. Fresh urine is treated with a mixture of baryta 
water and nitrate of barium in a decanting jar, till all of the 
phosphates and sulphates are precipitated. When the precipi- 
tate has thoroughly settled, the clear fluid is removed with a 
siphon, and evaporated in a large porcelain dish over a gas 
stove. The latter not only renders water baths for this sort of 
work superfluous, but also allows of a much quicker evapo- 
ration without ever bringing the fluid to boiling. The syrupy 
mother liquor, from about fifty liters of urine, is poured off 
from the salts crystallized out after cooling, diluted to four or 
five liters, treated with about a pound of ammonia, and precipi- 
tated with an ammoniacal solution of nitrate of silver. As soon 
as the precipitate is settled, the supernatant fluid is removed 
with a siphon, the silver compound is collected on a filter and 
washed with distilled water until the filtrate no longer reacts 
with chlorine. When this point is reached, the filter is laid on 
blotting paper and kept there until the moist precipitate can 
be readily removed, it is then put into a flask and dissolved by 
boiling in as little nitric acid of a specific gravity of 1"1 as pos- 
sible. In most cases a complete solution follows, and only a 
few flocculi of chloride of silver remain behind ; the heat is 
continued till the fluid, at first very dark colored, has become 
light yellow. Soon yellow flakes of nitrate of xantliin silver 
oxide separate from the filtrate. Since, however, the silver 
compound of xantliin separates from the nitric acid solution 
much more slowly than the corresponding sarkin compound, 
the fluid is allowed to stand at least eight to twelve days ; from 
the first a too great excess of nitric acid should be avoided. 
The nitrate of xanthin silver oxide is collected on a filter, 
washed and digested, for the removal of nitric acid, with ammo- 
nio-nitrate of silver. After washing again, the yellow-colored 
silver compound is suspended in water, and, after the addition 
of a little hydrochloric acid, heated to boiling and decomjDOsed 
by sulphuretted hydrogen. The filtrate which is • still colored 
yellow is decolorized completely by treating it with some well- 
extracted animal charcoal, and after concentration the chloride 



32 ANALYSIS OF THE UUmE. 

of xantliin separates in small hard crystals. By repeatedly 
evaporating tlie chloride of xanthin with ammonia, and finally 
washing out the chloride of ammonium with cold water, pure 
xanthin is obtained. The amount obtained is very small — with 
less than one or two hundred j)ounds of urine the work should 
not be undertaken. The nitric acid solution, from which the 
nitrate of xanthin silver oxide was crystallized, contains the rest 
of the xanthin compound, and, as I believe, other silver com- 
pounds also. On the addition of ammonia, a considerable 
amount of gelatinous, yellow precipitate falls, with which a 
considerable amount of the silver xanthin compound is always 
mixed. 

2. Kreatinin. The ammoniacal mother liquor, from which the 
xanthin was precijDitated by nitrate of silver, is heated again on 
the gas stove, when the ammonia escapes, and the excess of sil- 
ver added separates at the same time. If the fluid no longer 
smells of ammonia it is filtered, and the clear fluid evaporated 
to a syrup. After cooling, about an equal volume of alcohol is 
added, it is alloAved to stand twenty-four hours, decanted from 
the nearly crystallized salts, and mixed with a concentrated 
neutral alcoholic solution of chloride of zinc, when, after a short 
time, very pure, faintly yellow kreatinin chloride of zinc preci- 
j)itates, which is used for obtaining kreatin and kreatinin by 
the familiar method with freshly precipitated hydrated oxide of 
lead, etc. 

3. Urea. The alcoholic mother liquor, from which kreatinin 
was precipitated, is mixed with an equal volume of pure nitric 
acid of specific gravity 1*2, and allowed to stand in the cold 
twenty-four hours to crystallize out the nitrate of urea. The 
crystalline mass is placed on porous tiles, alloAved to dry, dis- 
solved in water and boiled with pure animal charcoal. The 
filtrate remains yellow, and after evaporation deposits large 
amounts of yellow nitrate of urea. All of the products of crystal- 
lization are dissolved in water, and the boiling solution treated 
with small amounts of permanganate of potassium until it has be- 
come absolutely colorless. After evaporation the nitrate of urea 
crystallizes out perfectly colorless. To obtain pure urea, the 
nitrate is finally decomposed by freshly precipitated carbonate 
of barium, evaporated, most of the nitrate of barium allowed 
to crystallize out, the mother liquor brought to complete dry- 



NORMAL CONSTITUENTS OF URINE, ORGANIC. 33 

ness, and the urea extracted, v/liile cold, with five times its 
amount of alcohol (93 per cent.). After distilling off the alco- 
hol, the urea separates in masses of pure crystals. 



APPENDIX. 

Hypoxantliin (SarHn), 

Hypoxanthin, or sarkin, e.H^N.O [C,oH,:N',0,], which is of con- 
stant occurrence in the juice of muscle, has hitherto not been 
found in the urine with certainty, although Salkowsky succeeded 
in separating a body from normal as well as leuksemic urine, 
which corresponded with sarkin in its characteristics, except 
in a few particulars. Sarkin was certainly detected in the me- 
dulla of bone from leukgemic persons by Salkowsky, and also 
in fifteen pounds of normal calves' bones. The method above 
described by me for separating xanthin, serves for detecting 
the sarkin, the nitrate of silver compound of which differs from 
the corresponding xanthin one only by its being very much 
less soluble in nitric acid. The masses which separate imme- 
diately on cooling from the boiling nitric acid solution of the 
silver compound, will have some sarkin present. To separate 
it with certainty it is recrystallized, after the addition of one 
cubic centimeter of the nitrate of silver solution, once or twice 
from hot nitric acid, and that portion which first separates is 
collected on a filter, washed, and digested for a time with an 
ammoniacal silver solution to remove the nitric acid, filtered, 
washed, the precipitate suspended in water, heated to boiling, 
and decomposed with sulphuretted hydrogen. The colorless 
filtrate leaves, after evaporation, pure crystallized sarkin. 

Sarkin is distinguished from xanthin, especially in the fol- 
lowing particulars : 

1. The nitrate of sarkin silver oxide completely separates 
from hot nitric acid immediately on cooling. The compound 
shows, under the microscope, long colorless needles, which do 
not blacken on exposure to light. The corresponding xanthin 
compound separates, after a long time, in scaly masses.^ 

2. Pure sarkin, after careful evaporation with nitric acid, 

* Zeitsclirift fiir analyt. Chemie, Band 6, p. 33. 
3 



34 ANALYSIS OF THE URmE. 

does not furnisli a deep-yellow residue, but an almost colorless, 
or, at most, a liglit-yellow one, wliich, on tlie addition of hy- 
drate of sodium, becomes somewat darker, but not, as in the 
case of xanthin and guanin, red yellow; 

3. Sarkin does not give, with hydrate of sodium and calcic 
hypochlorite, a green color. 

4. Sarkin separates from hot water in a crystalline form 
xanthin, on the other hand, amorphous. (See § 5, B.) 

Weidel found a new base in Liebig's meat extract, carnin, 
038^4^3 + HoO, which yields, on heating with nitric acid, ni- 
trate of sarkin, together with some oxalic acid. Carnin con- 
tains, therefore, the elements of sarkin and of acetic acid : 

Carnin = GJIs^A 
Sarkin r=: G5H,:N",a 
Difference -— C0H4O0 = acetic acid ; 

but on account of its stability when treated with baryta water, 
it is not to be regarded as acetate of sarkin. 

If carnin or sarkin is heated with fresh chlorine water and 
a trace of nitric acid until the slight evolution of gas has ceased, 
then evaporated to dryness on a water bath, and the white 
residue exposed under a receiver to ammonia vapor, in a short 
time a dark rose-red color appears. 

The formula of carnin differs from that of theobromin only 
in possessing one atom more of oxygen. 

F. Baumstark " found first in the urine of a dog fed on 
benzoic acid, then in icteric, and finally, also in normal human 
urine, a new crystalline body by the following procedure : 

The urine, carefully concentrated to a syrup on the water 
bath, or over a gas stove, is, while it is still warm, mixed with 
large quantities of alcohol, the spirit is distilled off from the 
filtered alcoholic solution, the hip^^uric acid removed from the 
residue after acidifying with hydrochloric acid by shaking with 
ether, and the fluid thus freed after supersaturation with am- 
monia, completely precipitated with basic acetate of lead. The 
fluid filtered from the lead precipitate is freed from surplus 
lead by sulphuretted hydrogen, and evaporated to a syrup. 

* Bericlit. der deutscli. cliem. Gesellscliaft, Band G, p. 883. Annal. der Cliemie, 
Band 173, p. 893. 



NORMAL CONSTITUENTS OF URINE, ORGANIC. 35 

The new body, together with urea, separates from this residue 
after long standing, and remains insohible on treating the crys- 
talline mass with alcohol. The new hitherto nameless body 
crystallizes out of hot water in w^hite prisms, similar to those 
of hippuric acid, which melt at over 250° C. Heated on plati- 
num foil, thick white fumes are evolved with dissemination of 
a peculiar odor. Heated in a small tube, the body yields an 
inflammable gas, which smells like ethylamin and blues litmus. 
The crystals dissolve with tolerable readiness in hot water, 
with difficulty in cold water and alcohol. They are insoluble 
in absolute alcohol and ether. 

Analysis gave the formula ^'sHgNgO (CoHsNaOs). It forms 
readily soluble salts with acids, but no compounds with bases. 
The solution is precipitated by mercuric nitrate. Lactic and 
paralactic acids form on treating it with nitrous acid ; boiling- 
it with baryta water evolves at first one-half of the nitrogen in 
the form of ammonia, and afterwards the rest as ethylamin with 
separation of carbonate of barium. 



§. 6. Ukic 

: €,H,NA 
[C,oH,N,OJ ^ 


Acid. 

- Carbon 
Hydrogen 
Nitrogen 

^ Oxygen 


35 '72 

2-38 

33-33 

28-57 



100-00 

A. Presence. Uric acid is found in the urine of all classes of 
animals, and occurs even in the very lowest orders. The excre- 
ment of birds (guano), snails, reptiles, and insects is rich in 
uric acid. Besides in the urine, it was detected also in normal 
blood of hens, by Meissner, and after extirpation of the kidneys 
by Strahl and Lieberkiihn "^ and recently by Garrod.t Accord- 
ing to the latter, it appears constantly increased in the blood 
in gout. It has further been found in the spleen, lung tissue^ 
muscular juice of the heart, the pancreas, brain, and liver, and 
finally in gouty deposits. E. Bender % found on the surfaces 

* Strati and Lieberkiilin. Harnsaure im Blute, etc., Berlin, 1848. 
f Prager Vierteljahressclirift, Band 5, S. 4, Abth. II., p. 13. 
X Journ, fiir prac. Chemie, 1866, III., p. 254. 



36 ANALYSIS OF THE URINE. 

of the face, stomach, and liver of a body exhumed after two 
months' burial, small white spots, which consisted of uric acicl 
crystals. 

The amount of uric acid in human urine is less dependent on 
the food taken, as is the case with urea, than on special inter- 
nal conditions of the economy. Under normal conditions, ac- 
cording to Becquerel, 0495 to 0*557 grams of uric acid are 
eliminated by a healthy man in twenty-four hours. According 
to my own experiments, instituted on a powerful healthy young 
man of twenty-three years of age, there was an average secretion 
of 36'4 grams of urea and 0*827 grams of uric acid in 2,000 cc. 
of urine in twenty-four hours. Further observations have shown 
me, however, that in the normal condition the amount of uric 
acid may vary considerably, and may fluctuate within twenty- 
four hours between 0*2 and 1 gram. According to Eanke, 
the proj)ortion of uric acid to urea varies from 1 : 50 to 1 : 80 in 
twenty-four hours. An increase of uric acid results, first of all, 
from disturbed digestion, as well as generally insufficient nutri- 
tion. Moreover, it is found to be increased in all febrile condi- 
tions, and especially in affections of the respiratory organs 
and disturbances of the circulation. In a case of leukaemia 
Salkowsky '"' found, during a series of observations extending 
over thirty days, that the uric acid was permanently increased, 
not alone in percentage, but also absolutely, especially in rela- 
tion to the urea. An average of thirty estimations gave a pro- 
portion of uric acid to urea of 1 : 16-3, which is more than a 
threefold increase. 

If uric acid is taken into the body it is decomposed normally 
into carbonic acid and urea, but yields also oxalic acid, when- 
ever the process of oxidation has undergone a retardation in 
any way. 

B. Prejjaration.—l. From Human Urine. Freshly filtered 
morning urine is treated with hydrochloric acid (20 cc. to 1 
liter of urine), and allowed to stand forty-eight hours. The 
uric acid will be found separated in more or less deeply colored 
crystals, which are specially adapted for microscopic study. 

2. From Excrement of Seiyents. The excreta of serpents are 
boiled with a solution of one part of potassic hydrate in twenty 



''^ Yircliow's Archiv, Band 50. 



NORMAL CONSTITUENTS OF UMINE, ORGANIC. 37 

parts of water until the ammoniacal odor lias disappeared. Car- 
bonic anhydride is conducted into the filtered solution until it is 
nearly neutral, and the acid urate of potassium, which is thus 
separated, is collected and washed with water. After washing, 
the potassium salt is dissolved in potassic hydrate, and the 
solution filtered into dilute hydrochloric acid, care being taken 
that the latter is always present in excess ; the precipitate is 
pure uric acid, which, after washing and drying, is obtained as 
a delicate light powder. 

C. 3Iicroscopic Properties. Uric acid appears in many different 
forms under the microscope, chiefly, however, as smooth tables 
of rhombic form. These are sometimes colored, are always of 
extraordinary transparency, and vary in size — often being by no 
means small. The tables are frequently modified, so that spin- 
dle-shaped crystals are formed by the rounding off of the obtuse 
angles, with which are mixed short barrel-shaj)ed cylinders. 
Frequently, however, six-sided plates, rectangular tables, or 
rectangular four-sided prisms with abrupt terminations ap- 
pear ; these often lie collected together in peculiar rosettes. 
Besides these, other modifications occur, as saw-shaped, fan- 
shaped, or tooth-shaped crystals. (Plate I., figs. 2 and 3; Plate 
II., fig. 4; Plate III., fig. 1.) 

I succeeded in obtaining very manifold forms of uric acid, 
whose character could readily be seen by comparison with 
Funke's plates, by treating a normal urine with different amounts 
of hydrochloric acid. If the nature of any crystal is doubtful, 
however, it is very easy to bring it into the usual form ; it is 
dissolved on an object glass in a small amount of potassic hy- 
drate, and a drop of hydrochloric acid is added, when the usual 
tabular and spindle forms are seen to occur. 

D. Chemical Properties. Pure uric acid prepared from the ex- 
crement of serpents forms white, very light, delicate-feeling 
crystalline scales, which, seen under the microscope, show the 
above-described forms. It is without taste and odor, is very 
difficultly soluble in water (one part of uric acid requires four- 
teen to fifteen thousand parts of cold water, and eighteen to 
nineteen parts of hot water), the solutions obtained do not red- 
den litmus. In dilute hydrochloric acid it is quite as insoluble, 
and is not at all soluble in alcohol and ether. It is readily 
soluble in concentrated sulphuric acid without decomposition, 



38 AJ^ALYSIS OF THE UltmE. 

but is precipitated from this solution again by diluting with 
water. 

1. It is quite readily soluble in a solution of phosphate of 
sodium as well as in that of many othor salts of the alkalies. It 
takes from these salts a part of the base, with which it com- 
bines, and thus gives rise to the formation of acid salts. It is 
contained in the urine in this form, together with the acid 
phosphate of sodium, which is the chief source of the acid re- 
action of urine. It is easy to obtain a fluid similar to urine, 
with an acid reaction, by dissolving uric acid in a warm solution 
of jDhosphate of sodium, and from this fluid crystals of urate 
of sodium are deposited on sufficient concentration. (For the 
separation of the latter from the urine, see Sediments.) 

If the acid solution, which results from dissolving uric acid 
in phosj)hate of sodium, is allowed to stand a long time at a 
temperature of 20"" to 30'" C, after a few days bacteria form, the 
acid reaction diminishes, and the fluid gradually becomes alka- 
line. After eight to fourteen days all of the uric acid is decom- 
posed, and the fluid contains urea and carbonate of ammonium. 
Other products, as allantoin, oxalic acid, etc., do not aj)pear to 
be formed in this decom230sition. (Lex.) 

2. If uric acid is heated in a glass tube it is decomposed, 
without, however, previously melting. It breaks up into urea, 
cyanuric acid which forms a sublimate, hydrocyanic acid, and a 
little carbonate of ammonium, which can be recognized by its 
odor. In addition peculiar oily products are observed, and a 
porous carbon containing nitrogen is left behind. 

3. If uric acid, made into a pulp with water, is boiled with 
peroxide of lead, it decomposes into four bodies : carbonic an- 
hydride, allantoin, urea, and oxalic acid. The allantoin which 
is naturally present in the urine of calves, as well as the urea, 
can be easily obtained by crystallization and recognized, the 
oxalic acid remains in combination with the lead, while the 
carbonic anhydride escapes with effervescence. According to 
Pelouze a little allanturic acid is formed also. It is not impro- 
bable that the urea which occurs in this decomposition is a 
further product of the oxidation of allantoin, and the carbonic 
acid a product of the oxidation of oxalic acid, so that the sim- 
plest decomposition of uric acid by peroxide of lead is into 
allantoin (O4H0N4O3) [CsHeNiOJ and oxalic acid. 



NORMAL CONSTITUENTS OF URINE, ORGANIC. 39 

4 If lijdriodic or hydro chloric acid is allowed to act on uric 
acid in sealed tubes at 160^ to ITO"" C, it decomposes into gly- 
cocoll, carbonic anhydride, and ammonia. (Strecker.) On pro- 
longed heating of uric acid with double its weight of concen- 
trated sulphuric acid, in addition to giycocoll, a body similar to 
xanthin (pseudoxanthin) and hydurilic acid result. (O. Schult- 
zen and Filehne.) 

By this formation of giycocoll from uric acid, a close chemi- 
cal relationship between uric acid and hippuric acid, the char- 
acteristic constituents of the urine of carnivora and herbivora, 
is foreshadowed."* 

5. Permanganate of potassium and ozone act very energeti- 
cally on uric acid ; allantoin, carbonic anhydride, oxalic acid, 
and urea are formed, or by ozone in an alkaline solution, urea, 
ammonia, oxalic acid, and carbonic anhydride. 

6. If one part of uric acid is gradually added to four parts of 
concentrated nitric acid (specific gravity = 1*420), it is dissolved 
with effervescence, and finally the whole fluid solidifies to a crys- 
talline pulp. The uric acid at the same time decomposes into 
alloxan (04X12^2^4) [C8H2N2OS] and urea ; the first separates in 
the form of crystals, the latter by the simultaneous formation 
of nitrous acid decomposes immediately into carbonic acid and 
nitrogen, which escape and cause the efi'ervescence of the fluid. 

7. If reducing agents, such as, for example, sulphuretted hy- 
drogen, hydrogen gas, etc., are allowed to act on the solution of 
alloxan, very soon crystals of a new body, alloxautin, se23arate 
(CsHioN'4010) [OigHioNjO^o]. This body is much more difficult 
to dissolve than alloxan, it crystallizes in oblique four-sided 
prisms, and becomes red when exposed to ammonia vapor. 

Alloxan and alloxantin give rise to the most important uric 
acid reaction. If a solution of alloxan and alloxantin is treated 
with ammonia, it becomes purple red, and after standing a time 
crystals of murexid are deposited. These form four-sided 
prisms, which reflect light of a cantharides-green color ; tritu- 
rated they form a brown powder, and dissolve in water with a 
deep purple color. It always serves for the detection of uric 
acid. 



" Annal. der Chemie und Pliarm., Band 146, p. 142. Chem. Centralblatt, 1868, 
p. 499. 



40 ANALYSIS OF THE UEmE. 

8. Uric acid treated with moderately dilute nitric acid dis- 
solves, and alloxantin is found as the chief product of the reac- 
tion. If we carefully evaporate this solution almost to dryness, 
alloxan is formed from a part of the alloxantin by the further 
action of nitric acid. If now ammonia is allowed to act on the 
mixture, the beautiful color of murexid is produced. This 
color of murexid is rendered purple blue, by caustic potassa. 
By means of this reaction the smallest amounts of uric acid are 
readily detected. If the residue is treated immediately with 
potassic or sodic hydrate, instead of with ammonia, a magnifi- 
cent purple-violet solution is obtained, which, however, becomes 
paler on heating, and finally, before the fluid is entirely evapo- 
rated, loses its beautiful color completely. (Distinction from 
xanthin, see Xanthin.) 

According to Hardy, modified red alloxan forms first on 
evaporating uric acid with nitric acid, and on the addition of 
ammonia it is changed into red isoalloxanate of ammonium. 

9. Uric acid forms salts with the bases which are more or 
less readily soluble in water ; the most soluble is the lithium 
salt. Crystalline uric acid is separated from these solutions on 
the addition of hydrochloric acid, acetic acid, etc. In concen- 
trated solutions the separation takes place immediately ; in 
dilute, as for example urine, only after long standing, as twenty- 
four or thirty-six hours. The crystals are readily recognized 
under the microscope. For the different salts, see Sediments. 

10. An alkaline solution of uric acid reduces nitrate of silver 
immediately, even in the cold. If a trace of uric acid is dis- 
solved in a solution of sodic carbonate, and a paper on which a 
drop of nitrate of silver solution has been allowed to spread is 
wet with it, a dark spot immediately forms, even when the uric 
acid is diluted one-thousand-times, but still smaller quantities, 
even to one five-hundred- thousandth of a gram, after a few 
seconds show a distinct yellow reaction without its being neces- 
sary to heat. (Schiff.) 

11. If a solution of uric acid in potassic hydrate is added to an 
alkaline copper solution, a white precipitate of cupreous urate 
is formed. If the latter is heated to boiling with an excess of 
the solution of copper, the uric acid oxidizes, and red cupreous 
oxide separates, while the products of the oxidation of uric acid, 
allantoin, urea^ and oxalic acid, remain in solution. 



NORMAL CONSTITUENTS OF URINE, ORGANIC. 41 

12. If a bromidized alkaline solution of liypoclilorite of so- 
dium is allowed to act on uric acid, an intense rose-red fluid is 
formed. The color disappears after a time, especially if more 
of the bromine solution is added. (Dietrich.)* 

E. Detection. It is to be noticed here that urine which is 
undergoing acid fermentation frequently deposits uric acid in 
more or less deeply colored crystals. In diabetic urine, espe- 
cially, one finds not infrequently after a short time all of the 
uric acid as a red, sandy, crystalline powder on the bottom of 
the glass. 

1. 100 to 200 cc. of urine are evaporated in a porcelain evapo- 
rating dish on a water bath. If the urine contains albumen, it 
must first be coagulated by boiling after the addition of a drop 
of acetic acid, filtered, and the filtrate evaporated to a syrupy 
consistency. By frequently treating with alcohol the urea is 
extracted from the residue together with the extractive matters 
and the salts soluble in alcohol; the uric acid, on the other 
hand, remains behind with the insoluble salts and mucus. The 
salts are removed by pouring over it a small amount of dilute 
hydrochloric acid, and uric acid is obtained alone with a small 
amount of mucus. The following tests are to be employed to 
insure its perfect recognition: 

a. A few drops of nitric acid are poured over a small portion 
in a watch glass. The specimen dissolves more or less com- 
pletely on warming, and after evaporating on a water bath 
leaves a reddish residue behind. If this residue is moistened 
with dilute ammonia (one part to ten of water), the purple-red 
murexid appears instantly, which, by addition of a drop of 
potassic hydrate, becomes purple blue. If the amount of uric 
acid present is very small, an excess of ammonia can very 
easily hinder the reaction, therefore it is safer to bring a glass 
rod moistened with ammonia near it, and to allow the ammo- 
nia vapor to blow over the residue. The test thus performed 
will react certainly and beautifully with mere traces of uric 
acid. 

b. The remainder is dissolved in a few drops of potassic 
hydrate, in which the mucus will remain undissolved. From 
this solution of urate of potassium the uric acid is precipitated 

* Zeitscrift fiir analyt, Chem., Band 4, p. 176. 



42 ANALYSIS OF THE URINE. 

in a crystalline form by tlie addition of liydrocliloric acid, and 
is recognized under the microscope. 

2. The following method is simpler : About 200 cc. of urine 
are treated in a beaker with 5 cc. of hydrochloric acid, and 
allowed to stand twenty-four to forty-eight hours. At the end 
of this time the uric acid will be found separated in the form of 
colored crystals, which partly float on the surface, and partly 
are deposited on the sides and bottom of the glass. An exami- 
nation, under the microscope, as well as a test of the filtered 
crystals, with nitric acid and ammonia, will permit its easy 
recognition as uric acid. 

3. If there is only a small amount of fluid to test for uric 
acid, it is to be poured on a shallow watch glass, and with from 
four to eight grams, six to twelve drops of strong acetic acid 
are to be added, and after a thread about an inch long is laid 
in the fluid, it is to be allowed to stand eighteen or twenty-four 
hours, at a temperature at most of 16"" to 20° C. At the end of 
this time the uric acid will have separated in crystals on the 
thread, which must, therefore, be examined microscopically. 
This method is particularly fitted to test the blood-serum of 
gouty patients for uric acid. (Garrod.) 



§ 7. OxAT,UBic Acid. 






r Carbon 


27-27 


Formula : 08H4N,a4 , 


Hydrogen 


3-03 


[OeH,^,0,] 


Nitrogen 


21-21 




^ Oxygen 


48-49 



100-00 

A. Presence. Schunk^ first proved the occurrence of oxaluric 
acid, combined with ammonia, in normal urine. This discovery 
renders it more than probable that other members also of 
the large series of uric acid derivatives occur in normal or 
pathological urine, whereby additional information in reference 
to physiology and pathology may be obtained. 

Oxaluric acid stands in close relation to uric acid, xanthin, 

•'^ Proceed, of the Eoyal Society, vol. 16, p. 140. Zeitschrift fiir analyt. 
Chem., Band 6, p. 499, and Band 7, p. 325. 



NORMAL CONSTITUENTS OF URINE, ORGANIC. 43 

and gnaiiin, and also to urea. Uric acid, treated witli nitric 
acid, yields first urea and alloxan ; tlie latter by further oxida- 
tion gives, with the development of carbonic acid, parabanic 
acid, which is also obtained by treating guanin and xanthin 
with chlorate of potassium and hydrochloric acid. Parabanic 
acid becomes oxaluric acid by absorbing water, and this, on 
boiling with water, splits up into urea and oxalic acid. 

The following equations shoAV the gradual decomposition of 
uric acid into urea, oxaluric acid, carbonic acid, and water : 

1. o,H,]^,03 + o + H,a =G,H,N A+0H4]sr,a 

• [C,oH4N40. + 20 + 2H0 = CsH^N^Os + C|H4:Nr,0,] 

(Uric acid) (Alloxan) (Urea). 

2. 04H2N,A + O = GaH^^^.Os + CO2 

[0,H,N,08 + 20 = CeH.N,Oe + 2C0 J 

(Alloxan) (Parabanic acid). 

3. OsH^N.Os + H,a = e,H4^^oa4 

[CeHeN-,Oo + 2H0 = CeH4]^,0,] 
(Parabanic acid) (Oxaluric acid). 

4. G3H4lSrA + H,a=OH4N,0 + GoHo04 

[CcH4N,03 + 2H0 = GMJsSy. + C4H,0 J 

(Oxaluric acid) (Urea) (Oxalic acid). 

5. GJI A + O = 200.2 + H2O 
[C4H A -f 20 =400^ + 2H0] 
(Oxalic acid) (Carb. acid) (Water). 

B. Preparation. A solution of uric acid in warm very dilute 
nitric acid, when treated with ammonia, immediately after cool- 
ing, yields, on evaporation, crystals of oxalurate of ammonium. 
The same salt is obtained by boiling parabanic acid with am- 
monia, and evaporating the solution. Hydrochloric acid sepa- 
rates the oxaluric acid from a concentrated solution of oxalurate 
of ammonium, as a light, white, crystalline powder. 

C. Microscopic Properties. If a drop of a solution of pure 
oxalurate of ammonium is evaporated on an object glass un- 
der the microscope, long prisms, with pointed ends, are seen, 
which unite to form beautiful double tufts, or more or less com- 
plete rosettes. If the salt is not perfectly pure, the tufts of 
needles remain small, and form spherical aggregations which 



44 ANALYSIS OF THE URINE. 

are studded on the periphery with fine, prominent, crystalline 
needles. If a drop of nitric acid is brought in contact with 
such crystalline aggregations, the rosettes of prismatic crystals 
change, while still maintaining their opposed position, into a 
warty clump of oxaluric acid crystals. 

If a solution of oxalurate of ammonium is treated with nitric 
acid, a Avhite crystalline powder separates according to the con- 
centration, either immediately or after long standing, consisting 
chiefly of indistinctly defined oxaluric acid crystals. After short 
or long standing in the nitric acid fluid, sometimes only after 
several days, the separated oxaluric acid disappears again, and 
a drop of this solution now allowed to evaporate on an object 
glass readily shows the characteristic forms of nitrate of urea 
under the microscope. 

D. Chemical Properties. Free oxaluric acid is a white, crys- 
talline powder having an acid taste, very difficultly soluble in 
water. The oxalurate of the alkalies, like that of ammonium, 
is soluble in water ; the other salts, on the other hand, are dif- 
ficultly soluble or insoluble. 

1. An aqueous, tolerably dilute solution of oxalurate of am- 
monium, treated with chloride of calcium and ammonium, does 
not give rise to a jDrecipitate ; the fluid remains perfectly clear. 
If the mixture is then warmed, there occurs very soon, far be- 
fore the boiling point, a cloudiness, and calcic oxalate separates 
in large quantities. This reaction, gives, doubtless, the most 
delicate test, and with it incredibly small amounts of oxaluric 
acid can be detected with the aid of the microscope. If the 
solution was too concentrated, the precipitated calcic oxalate 
will be amorphous. Dilute solutions, however, especially when 
the fluid contains coloring matters, etc. (as, for exarople, a di- 
lute solution of oxalurate of ammonium in urine), give, when 
treated in this way, a precipitate of calcic oxalate, insoluble in 
acetic acid, and showing under the microscope the most beauti- 
ful quadrilateral octahedra. If the microscopic examination 
should show no well-formed crystals of calcic oxalate, it is easy 
to bring the amorphous into the crystalline form. For this pur- 
pose the precipitate is allowed to settle, the fluid is decanted 
from it, and it is dissolved in one to two drops of hydrochloric 
acid. If then the hydrochloric acid solution is tolerably diluted, 
and carefully covered with a layer of ammonic hydrate, on quiet 



NORMAL CONSTITUENTS OF URINE, ORGANIC. 45 

standing, the two fluids gradually mix, and as soon as tlie calcic 
oxalate lias com^^letely separated again, the microscope will 
show a greater or less number of the most beautiful quadrilat- 
eral octahedra. With care this reaction never fails, and with 
the yery characteristic form of the calcic oxalate it is most deli- 
cate and decisive. 

2. If a solution of oxalurate of ammonium is boiled with 
hydrochloric acid, in a few minutes oxalic acid can be detected 
by adding ammonia and chloride of calcium. 

3. An aqueous solution of oxalurate of ammonium, with ni- 
trate of silver, does not give a precipitate immediately ; after a 
few minutes, however, fine crystalline needles separate, which 
on sufiicient concentration at last fill the whole fluid, and 
under the microscope appear as very fine hair-like needles, ar- 
ranged in stars and rosettes. The silver salt does not blacken 
on exposure to the light, and readily dissolves in ammonia. 
The ammoniacal solution does not become reduced by boil- 
ing. 

4. A tolerably concentrated solution of pure oxalurate of am- 
monium does not give a precipitate immediately when treated 
with sugar of lead solution. After a few minutes the mixture 
becomes cloudy, and oxalurate of lead separates as a heavy 
crystalline powder, which appears under high powers of the 
microscope, as very well formed four-sided prisms, with six end 
surfaces. If the oxalurate of ammonium is not quite pure, its 
aqueous, tolerably concentrated solution is treated with the 
lead salt, the precipitate which takes place immediately is fil- 
tered off, and the filtrate is left at rest, when the characteristic 
crystals will soon separate. According to my experience the 
lead salt in the crystalline form is more easily obtained from 
impure material than the silver salt. 

5. The addition of chloride of calcium or chloride of zinc 
to moderately concentrated solutions of oxalurate of ammonium 
causes crystalline deposits of the salts of these metals to sepa- 
rate after long standing; these also show very characteristic 
forms under the microscope. 

E. Detection. The urine is filtered through animal charcoal to 
separate the oxalurate of ammonium. This salt is retained by 
the charcoal, and can be withdrawn by boiling it with alcohol. 
I use the apparatus shown in the accompanying figure, which, 



46 



ANALYSIS OF THE URINE. 



Fig. 1. 



in fact, allows several liimdred liters of urine to be used with 
little oversight. The ajDparatus (fig. 1) is intelligible without 

a description ; the pipette, 
A, of about 400 cc. capaci- 
ty, is filled with finely gra- 
nulated animal charcoal, 
such as is used in sugar 
manufactories. The screw 
of the stop-cock, C, is reg- 
ulated so that the urine 
runs off in drops, and dur- 
ing twenty-four hours six- 
teen or twenty liters pass 
through the charcoal. If 
the decolorizing power of 
the charcoal, covered with 
a new piece of fine linen 
from time to time to catch 
the epithelium, etc., ceases, 
the pipette is emptied and 
filled with new charcoal, so 
that the filtration can be 
continued for weeks. 

The charcoal saturated 
W^ 'B with coloring matters, etc., 
is next w^ashed with dis- 
1^^^ tilled water, until the fil- 
trate no longer reacts for 
chlorine and phosphoric 
acid ; it is then dried in the air, and finally is repeatedly boiled 
with alcohol until the latter is no longer colored yellow. Wash- 
ing and boiling require some patience, yet may be successfully 
performed. The greater part of the alcohol is next distilled off 
from the golden-yellow alcoholic solution, the rest of the fluid is 
evaporated in a porcelain dish on a water bath, either in the open 
air or under a hood with a good draught, since a fearful urinous 
odor, which persistently sticks to the clothing, is evolved by it, 
such as I do not ever remember to have experienced in so great 
a degree in all my many labors with urine. On treating the resi- 
due with lukewarm water, a tenacious fatty mass remains be- 




NORMAL CONSTITUENTS OF URINE, ORGANIC. 47 

liind, in wliicli Scliunk lias found a crystalline fatty acid. Tlie 
aqueous brown solution, however, yields after evaporation a 
syrupy residue, from wliicli, after long standing in the cold, crys- 
talline oxalurate of ammonium separates. To shorten this pro- 
cess I have made use of dialysis through parchment with the 
best results. Even if the sej)aration is not absolutely complete, 
the sufficiently concentrated diffusate soon solidifies to a crys- 
talline mass. The rest of the syrupy mother liquor is extracted 
with absolute alcohol, the crystalline residue is washed with al- 
cohol a few times and then dissolved in hot water, the solution 
obtained is digested with a very small amount of purified animal 
charcoal, filtered, and the colorless filtrate evaporated, when on 
sufficient concentration pure oxalurate of ammonium separates. 
The yield is only very small, yet I obtained from 100 to 150 
liters of urine, according to the method described, a sufficient 
amount to recognize this interesting body by all of its character- 
istic qualities, and to com]3are it with the pure salt prepared 
from parabanic acid. 



8. HippuRic Acid. 



Formula : OgHgNO 



Carbon 60-34 
Hydrogen 5 -03 



[CsHgNOo] 1 Nitrogen 7-82 
[Oxygen 26-81 



100-00 



A. Presence. Hippuric acid is present chiefly in the urine of 
herbivora. It is found in human urine in normal as well as in 
abnormal conditions. Bence Jones found in the twenty-four 
hours' urine of a small man 0-32 grm. of hippuric acid and 0-5 
grm. of uric acid ; in a heavy man, 0-42 grm. of hippuric acid, 
and 0-82 grm. of uric acid. Before meals the urine of both 
persons always contained less hippuric acid and also less uric 
acid in one thousand parts of urine than after meals. Thudi- 
cum found on the average in the urine of an adult in twenty- 
four hours 0-169 to 0-315'grm., and even as much as 1*0 of hip- 
puric acid. After taking plums the twenty-four hours' amount 
increased to 2-212 grm. Hallwachs obtained from the twenty- 



48 ANALYSIS OF THE UBINE. 

four hours' amount of urine of different persons, even in a pre- 
ponderance of meat diet, nearly I'O grm. of hippuric acid. 

Hippuric acid is found to be increased by a purely vegetable 
diet, especially after taking plums, red whortleberries, mulber- 
ries, asparagus, and further, after the internal use of benzoic 
acid, oil of bitter almonds, toluol, cinnamic acid, kinic acid, 
etc. Succinic acid, on the contrary, causes no increase of hip- 
puric acid, according to Hallwachs, but according to Meissner 
is eliminated with the urine unchanged. In several diseases, 
especially in high fevers and in diabetes, an increased secretion 
of hippuric acid appears to occur. Besides in the urine, hip- 
puric acid has been detected in small amount in the suprarenal 
capsules of the ox, in diseased human blood, and also in icthy- 
osis scales. The source of hippuric acid in the urine may be 
twofold; first, bodies may be ingested with the food which are 
converted into hipj^uric acid in the economy. Hallwachs was 
unable to find benzoic acid in the ordinary grass fodder of the 
cow, but Zwenger and Siebert found in bilberry bushes toler- 
able quantities of kinic acid, as did also Schwarz and Oeliren 
in different sorts of galium ; we know that kinic acid is changed 
into hippuric acid in the economy. If kinic acid is wide-spread 
in the vegetable kingdom, which can scarcely be doubted, the 
great richness of the urine of herbivora in hippuric acid is 
thereby very simply explained. But in the oxidation of albu- 
men in alkaline solution with permanganate of potassium, con- 
siderable amounts of benzoic acid appear, wherefore it is more 
than probable that at least a part of the hip]3uric acid discharged 
with the urine is also formed by the metamorphosis of nitro- 
genous constituents of the body."^ 

According to the investigations of Meissner and Joly,t the 
urine of rabbits, after being fed on meadow hay and clover, con- 
tains much hippuric acid as wellas urea. The former almost 
entirely disappears from the urine, however, after exclusive 
feeding with carrots {Daucus carota), and is immediately re- 
placed by succinic acid to such an extent that benzoic acid 
does not appear. Meissner and Joly arrive at the conclusion 

* Meissner and Sliepard, Untersuchungen iiber das Entstehen der Hippur- 
saure, Hannover beiHalin, 1866. J. Erdmann, Cliem. Centralblatt, 1866, p. 897. 

f Zeitsclirift fur Cliem., Neue Folge, Band I., p. 330. Cliem. Centralblatt, 
1866, p. 239. 



NORMAL CONSTITUENTS OF URINE, ORGANIC. 49 

tliat the formation of liippuric acid, and what appears to be 
the chief thing, of benzoic acid, is directly dependent on the 
character of the food, and is not a characteristic of metamor- 
phosis in the herbivorous organism independent of the charac- 
ter of the food. According to the investigations of "Wildt, 
feeding on Leontodon taraxacum (dandelion) causes a not incon- 
siderable increase of hippuric acid in the urine. 

B. Microscopic Frojjerties. If a hot saturated solution of hip- 
puric acid is allowed to cool rapidly, the crystals under the 
microscope appear in the form of fine needles and hairs. It 
separates in regular, well-formed crystals, however, from a dilute 
cold saturated solution. It forms in this way, milk-white, semi- 
transparent, four-sided prisms and pillars, which are terminated 
by two or four surfaces. The typical form is always a vertical 
rhomboid prism. (Plate I., fig. 1.) Single crystals at times re- 
semble those of ammonio-magnesian phosphate, from which, 
however, hippuric acid is easily distinguishable by its chemical 
behavior. 

C. Freparation. Fresh horse or cow urine (5 to 6 liters) is 
boiled with an excess of milk of lime a few minutes, then 
filtered, the clear solution of hippurate of calcium is quickly 
evaporated to an eighth or a tenth of its original volume, and 
treated with hydrochloric acid. After twenty-four hours the 
hippuric acid is crystallized out, is dissolved again with milk of 
lime to purify it, and is allowed to crystallize again from the 
filtrate after the addition of hydrochloric acid. If it is not 
colorless even then, it can be treated in aqueous solution with 
well-burned animal charcoal. After the filtrate cools, it then 
separates in the form of colorless, transparent, long crystals. 
The mother liquor yields after evaporation a second crystal- 
lization. 

Loewe treats the fresh urine with sulphate of zinc, evaporates 
it together with the precipitate which takes place to one sixth, 
filters rapidly, and separates the hippuric acid from the filtrate 
by hydrochloric acid ; it is then to be recrystallized to purify 
it. This method gives a very pure preparation. 

An efficient procedure to purify colored hippuric acid is given 

by Gussmann. The crystals are dissolved in a sufficient 

amount of dilute sodic hydrate, and a solution of permanganate 

of potassium is added, drop by drop, to the fluid heated to boil- 

4 



50 AJVALYSIS OF THE URINE. 

ing, until a portion* filtered off gives a white precipitate witli 
liyclrocliloric acid. The entire filtrate, while still hot, is treated 
with a slight excess of hydrochloric acid and allowed to crys- 
tallize. 

D. Chemical Properties. — 1. Hi|)puric acid is odorless and has 
a slightly bitter taste. It requires six hundred parts of cold 
water to dissolve it, but much less hot water. Alcohol takes 
it up readily, ether with more difficulty but yet completely. 
The solutions redden litmus strongly. 

2. Hippuric acid heated in a small glass tube melts to an 
oily liquid. If it is allowed to cool it solidifies to a milk-white 
crystalline mass. On being heated more strongly it decom- 
poses, benzoic acid and benzoate of ammonium sublime, and at 
the same time is observed the formation of oily red drops, which 
diffuse a peculiar odor similar to that of fresh hay; after cool- 
ing they harden and are soluble in alcohol and ammonia, but 
not in water. If the heat is increased to nearly a red heat, an 
intense odor, like that of hydrocyanic acid, is developed, and a 
porous charcoal remains behind. This property is very char- 
acteristic of hippuric acid, whereby w^e can recognize it readily 
and distinguish it from uric acid and benzoic acid, with the 
latter of which it has very much resemblance. If in this dry 
distillation the heat is not raised above 250^ the hippuric acid 
yields only benzoic acid colored pale red by some foreign sub- 
stance, traces of hydrocyanic acid and a liquid body, nitro- 
benzol, which has the greatest resemblance in odor to oil of 
bitter almonds. 

3. If dilute mineral acids are allowed to act on hipj)uric acid 
it is not changed, but is, however, on heating with concentrated 
hydrochloric, sulphuric, or nitric acids. With these it under- 
goes a peculiar decomposition ; we find that crystalline benzoic 
acid has separated after cooling, and there remains dissolved in 
the fluid, combined with the mineral acid, a body which, when 
free, has a feebly acid reaction, glycocoU, OoH.NOi [0,H5N04] . 

[0,3H,]SrO, + 2H0 = C,,H,04 + C.H^NO,] 
(Hippuric acid) (Benzoic acid) (GlycocoU). 

4 In contact with fermenting or jDutrefying substances hip- 
puric acid becomes converted into benzoic acid, therefore it often 



NORMAL CONSTITUENTS OF URINE, ORGANIC. 51 

happens that it is no longer possible to separate it from old 
urine ; tlie benzoic acid formed volatilizes readily witli tlie 
steam as soon as a little hydrochloric acid is added to the nrine 
in evaporating it. 

6. If nitrous acid is allowed to act on hippuric acid, or nitric 
oxide gas is conducted into a solution of hippuric acid in nitric 
acid, it becomes, with the evolution of nitrogen, converted into 
an acid free from nitrogen, benzoglycolic acid, O0H3Q4 [OigHyOs]. 
The same decomposition occurs when hippuric acid is dissolved 
in an excess of dilute potassic hydrate, and the solution is 
treated in the cold with chlorine gas until no more nitrogen is 
evolved. 

6. Hippuric acid forms crystallizable salts with bases, and 
can be separated from solutions of its salts after sufficient con- 
centration by hydrochloric acid in the form of long needles. 

7. If boiling concentrated nitric acid is allowed to act on 
hippuric acid, the solution evaporated to dryness, and the resi- 
due introduced into a small glass tube and heated, an intense 
odor of nitrobenzol, similar to that of bitter almonds, is de- 
veloped. Benzoic acid gives the same reaction. "With cinna- 
mic acid the peculiar cinnamon odor conceals every other. 
Since even mere traces of nitrobenzol diffuse for a tolerably 
long time a powerful odor, this reaction is applicable to the de- 
tection of even very small amounts of hippuric acid. (Liicke.) 

Albumen, gluten, uric acid, grape sugar, salicin, salicyluric 
acid, choloidic acid, anisic acid, pyrogallic acid, kinic acid, pic- 
ric acid, naphtalin, phtalic acid, indigo, and isatin do not give 
this reaction. 

E. Detection. — 1. 800 to 1,000 cc. of urine are evaporated on a 
water bath almost to dryness, the residue is rubbed up with 
powdered baric sulphate, acidulated with hydrochloric acid, 
and extracted completely with alcohol. After neutralizing the 
alcoholic extract with sodic hydrate, the greatest part of the 
alcohol is distilled off, and the syrupy fluid which remains is, 
after the addition of oxalic acid, evaporated to dryness on the 
water bath with constant stirring. The dried mass is then suf- 
ficiently exhausted with large amounts of ether, to which some 
alcohol has been added, and the ethereal solution is distilled al- 
most to dryness. The crystalline residue is then treated, while 
hot, with milk of lime to remove the oxalic acid, filtered, the 



52 AJ^ALYSIS OF TUB URINE. 

filtrate evaporated to a very small volume, and tlien feebly acid- 
ulated with hydrochloric acid. After some time the hij)puric 
acid crystallizes out. The crystals are to l)e tested chemically 
and microscopically. Yery small amounts of hippuric acid are 
detected by the nitrobenzol reaction. (Chemical Properties, 7.) 

If, however, the urine is rich in hippuric acid, for example 
after taking benzoic acid, it is possible to obtain crystals of hip- 
puric acid from it after evaporation to a syrupy consistence, by 
treating it with a little hydrochloric acid ; these crystals are 
easily separated from the uric acid, which is deposited at the 
same time, by means of hot water. 

2. The following method of Meissner gives an easy and sure 
means of finding hippuric acid, and at the same time detecting 
any succinic acid present. 1,000 to 1,200 cc. of urine are precipi- 
tated carefully with strong baryta Avater, the excess of baryta 
water is removed by a few drops of sulphuric acid, of which an 
excess is to be avoided, and then filtered. The filtrate, accu- 
rately neutralized with hydrochloric acid, is then evaporated on 
a water bath to the consistency of a thick S3^rup, and the neutral 
residue, while still hot, is added to 150 or 200 cc. of absolute 
alcohol in a closed glass vessel. Any succinic acid salts are 
precipitated together with the chloride of sodium, etc., while 
the hippuric acid sails remain in solution. After repeated agi- 
tation, as soon as the precipitate has settled well the alcoholic 
solution is decanted, and the alcohol completely driven off on 
the water bath, the syrupy residue, which on cooling solidifies 
to a crystalline mass, is put into a closed vessel while it is still 
hot, acidulated with hydrochloric acid, and the hippuric acid 
extracted by shaking with not too small amounts of ether (100 
or 150 cc). After the ether is distilled off, the residue is di- 
luted with water, and heated to boiling with a little milk of 
lime. The hippuric acid separates from the concentrated fil- 
trate, after the addition of hydrochloric acid, in beautiful crys- 
talline rosettes ; they can be obtained entirely free from color 
by treating with pure animal charcoal. 

Succinic Acid. Since, according to the investigations of Meiss- 
ner and Shepard,"^* succinic acid also occurs in normal urine, 

* Meissner and Shepard, Untersucliungen iiber das Entstelien der Hippursa- 
ure, etc., Hannover, 1866. 



NORMAL CONSTITUENTS OF URINE, ORGANIC. 53 

regard must be paid to it in tlie qualitative analysis of urine/^' 
Meissner and Sliepard found succinic acid normally in the urine 
and in the blood : they found it in the urine, sweat, and saliva, 
after taking benzoic acid, and increased in the blood after the 
absorjjtion of kinic acid. Succinic acid taken internally, how- 
ever, causes no increased secretion of hippuric acid, but in not 
too small doses is eliminated unchanged in the urine. 

Since, according to Pasteur's and my own numerous investi- 
gations, wine and other fermented drinks contain not inconsid- 
erable quantities of succinic acid, and the latter, at least in 
part, goes over into the urine unchanged, we have a really fre- 
quent source for the occurrence of this acid in normal urine. 

Meissner and Joly t found considerable succinic acid in the 
urine, with exclusive meat and fatty diet ; a diminution, and 
even disappearance of it with vegetable diet, and generally with 
insufficient nourishment. Succinic acid is formed in the econ- 
omy also by the reduction of malic acid. It occurs in rabbits 
after feeding on carrots {Daiicus carota), also after the exhibi- 
tion of malate of calcium. Malate of sodium, however, yields 
only very little succinate, but becomes, for the most part, con- 
verted into the carbonate. 

Hilger and Koch found large amounts of succinic acid, to- 
gether with ammonia, after taking asparagus. There is no 
doubt that succinic acid and ammonia are formed from the as- 
paragin of the asparagus, which does not go over into the urine 
unchanged, but undergoes the same decomposition in the econ- 
omy as in the hands of the chemist. 

The saline mass precipitated from concentrated urine by ab- 
solute alcohol serves for its detection (see above, 2). After 
this has been thoroughly washed with alcohol, and finally 
pressed, it is dissolved in as little hot water as possible, hydro- 
chloric acid is added, and the succinic acid present is extracted 
by shaking with ether (100 to 150 cc). After distilling off the 
ether a brown mass remains, from which succinic acid crystal- 
lizes out with difficulty. I have found that treatment with nitric 
acid, by which the succinic acid is not attacked, is sufficient to 

■" Salkowski, from liis own numerous investigations, cannot acknowledge the 
occurrence of succinic acid in human urine as proved. Arcliiv der Physiolo- 
gic, Band 4, p. 95. 

f Loc. cit. 



54 ANALYSIS OF THE URINE. 

purify it. For tliis j)ui'P*^^®' ^-^^ ethereal extract is diluted with 
water, heated to boiling, and treated, while boiling, with pure 
nitric acid, drop bj drop, until the fluid has a barely percepti- 
ble yellow color. The succinic acid readily crystallizes from 
this solution, after concentration. The crystals are placed on 
blotting-paper, the mother liquor is absorbed, and the slightly 
yellow acid is used for the following reactions : 

1. A portion is sublimed in a small test tube. Succinic acid 
sublimes at 120^ to 130°. 

2. The remainder is dissolved in a little water, and the solu- 
tion obtained divided into two parts. One part is added to a 
mixture of alcohol, chloride of barium, and ammonia, when 
a white deposit of succinate of barium results. The second 
half is heated to boiling with an excess of carbonate of magne- 
sium, filtered, and treated with a few drojDS of a neutral solu- 
tion of ferric chloride, whereupon a voluminous brown precipi- 
tate of succinate of iron results. If the succinate of iron is 
decomposed, after washing, by heating with ammonia, the neu- 
tral filtrate gives, with a solution of nitrate of silver, a precipi- 
tate of succinate of silver. The silver salt is decomposed by 
sulphuretted hydrogen, and succinic acid is allowed to crystal- 
lize from the filtrate. (Funke, 2 ° Aufl., Taf. II., fig. 5.) ' 

3. Its behavior with the acetate of lead is very characteristic. 
The precipitate which first takes place dissolves readily and 
completely in an excess of the reagent, but it separates again 
on warming and shaking as a heavy crystalline powder. 

I succeeded by this method in detecting very small quanti- 
ties of succinic acid, after it had been added to 800 or 1,000 cc. 
of normal urine. 

Salkowsky prefers to extract the succinic acid with ether. 
For this purpose the urine is jDrecipitated with baryta, the 
excess of baryta is removed by sulphuric acid and evaporated. 
The concentrated solution is then strongly acidulated with sul- 
phuric acid and shaken several times with ether. It is puri- 
fied as above. 

4 Schultzen proposed with good result the following proce- 
dure for detecting hippuric acid in icteric urine. The urine is 
precipitated with acetate of lead, and the filtrate treated with 
sulphuretted hydrogen and then evaporated. The residue is 
extracted with alcohol, the extract evaporated, and the hippuric 



NORMAL CONSTITUENTS OF URINE, ORGANIC. 55 

acid remoYed from tlie residue, after addition of hydrochloric 
acid, by shaking with ether. After evaporating the ether it is' 
taken up with water, shaken with animal charcoal, and the fil- 
trate concentrated on the water bath, when quite pure crystals 
of hii3puric acid separate. If this is not the case, the residue 
is dissolved in water, and a drop of basic acetate of lead solu- 
tion added, whereby all of the extractive matters and any ben- 
zoic acid present are removed. The filtrate is freed from lead, 
evaporated, and after cooling treated with hydrochloric acid 
which separates the hij)puric acid. Without the previous pre- 
cipitation with sugar of lead, often only benzoic acid is obtained 
from icteric urine. 

§ 9. Phenol. 

(Carbolic acid, Phenylic acid, Phenylic alcohol.) 

^ T r^TT^ rC?.rbon 76-93 

h ormula : 4:^tiH6Q tt i ^ m 

rr TTOl 1 Hy^i'ogen 6-40 

[U,2-ti.U2j L Oxygen lG-67 



100-00 



A. Presence. Phenol was detected by "Wohler in the castor, 
and was later found by Stiideler, together with taurylic, damo- 
lic and damaluric acids as a constant constituent of the urine of 
the cow, human being, and horse." Only a very small quantity 
of this acid can be separated from human urine, and it is some- 
what doubtful whether this poisonous acid exists preformed in 
the urine, or is first formed during its isolation. According to 
recent investigations of Buliginsky ''^ carbolic acid is in fact a 
product of the decomposition of a yet unknown constituent of 
the urine, which is soluble in alcohol, and is not precipitated by 
the acetate or basic acetate of lead and ammonia, but yields 
carbolic acid by the action of dilute mineral acids. 

After the external as well as internal use of carbolic acid, 
according to Almen,t E. Salkowski,^: and others, it appears in 
the urine which frequently assumes an olive-green, deep dark- 
brown, or even black color, and in the same way, according to 

* Hoppe-Seyler, Med. Chem. Mittheiliing. , Heft 2, p. 234. 
•f- Nenes Jalirbucli d. Pharm., Band 34, p. 111. 
i Pfliiger's Ai'chiv, Band 5, p. 335. 



56 AJS'ALYSIS OF THE URINE. 

tlie inyestigations of Schnltzen and Naunjn/^ benzole changes 
into carbolic acid in the economy and aj)i3ears as such in the 
urine. 

B. Chemical Properties, In a completely anhydrous state 
phenylic acid crystallizes in long colorless needles, which melt 
at 37*5° C. and boil at 183° C. The acid smells like smoke, acts 
as a caustic, and i3 poisonous. It is difficultly soluble in water, 
easily soluble in alcohol and ether. The solution coagulates 
albumen, and has a strong antiseptic action. 

1. Nitric acid allowed to act on phenylic acid, forms first 
nitro-, then binitro-, and at last trinitro-phenylic acid, which is 
known under the common name of picric acid or Welter's bitter, 
and can be produced from indigo, salicin, etc., by treating with 
nitric acid. 

2. Ferric salts occasion in a solution of phenylic acid a violet 
color, playing into blue, which after a time changes to a dirty 
white turbidity. 

3. Nitrate of silver, and also mercuric oxide, are reduced by 
phenylic acid. 

4. A pine splinter, soaked in an aqueous solution of phenylic 
acid, and then dipped for an instant into dilute hydi^^ochloric 
acid, becomes colored deep blue in a few moments after expo- 
sure to the raj^s of the sun. The color obstinately resists the 
action of chlorine ; it becomes lighter to be sure, but returns 
again when the sjDlinter is dipped in dilute hydrochloric acid. 

5. An aqueous solution of phenylic acid, treated with ammo- 
nia and calcic hypochlorite, becomes, on heating, a beautiful 
blue color. (R. Lex.) 

To the fluid to be tested a quarter of its volume of ammonic 
hydrate is added, then a few drops of the calcic hypochlorite 
solution (one part of calcic hypochlorite to twenty parts of 
water), and the mixture is warmed a little, but not to boiling. 
If the phenol is in large quantity the blue color appears im- 
mediately ; if its quantity is small a few minutes to a quarter of 
an hour are required. 

Too high a temperature, and also too much calcic hypochlo- 
rite interferes with the reaction ; great care must be taken, 
therefore, in regard to the latter point. (Salkowski.) 

" Reichert's und Du Bois-Reymond's Arcliiv, 1867, Heft 3. 



NORMAL CONSTITUENTS OF URINE, ORGANIC. 57 

6. A solution of phenol, lieatecl to boiling with a solution 
of mercurous nitrate v/hich contains a trace of nitrous acid, 
gives an intense red mixture, and in concentrated solutions there 
is a rapid separation of metallic mercury. The reaction is still 
very distinct when diluted one part in sixty thousand. (Plugge.) 

7. A dilute aqueous solution of phenol, treated with an excess 
of bromine w^ater, gives rise immediately to a yellowish-white 
flocculent precipitate of tribrom-phenoL On sufficient addition 
of bromine water the precipitate disappears at first. The washed 
precipitate, treated in a test tube with a little sodium amalgam 
and water, and warmed, evolves, if the fluid is treated in a watch 
glass with dilute sulphuric acid, the characteristic odor of free 
phenol. This reaction is very delicate. (Landolt.) 

Together with phenylic acid Stadeler found a series of other 
acids very similar to it. These are : 

1. Taurylic Acid Q^HqO [CuHsOo] ? which would be isomeric 
with anisoL It differs from phenylic acid by its higher boil- 
ing point, and by giving, with concentrated sulphuric acid, a 
fixed compound which separates in delicate white tooth-shaped 
masses, which gradually collect together into spherical ones. 

2. Damaluric Acid G^His^o [O14H10O4]. This is an oily fluid 
similar to valerianic acid, heavier than water, but dissolving in 
it, however, to a slight extent, giving a strong acid reaction. 

This acid forms, with bases, well-characterized salts. The 
barium salt crystallizes in prisms, often joined together into 
tufts, which dissolve in water, giving a turmeric brown solution. 
The salt is fusible, and leaves behind, after ignition, carbonate 
of barium in the form of the original salt ; it contains 39*18 
per cent, of barium. 

The silver salt forms a white jDOw^ler, which does not change on 
exposure to light ; it contains 49*36 per cent, of oxide of silver. 

Basic acetate of lead also gives, in the solution of damaluric 
acid, a white precipitate, which appears under the microscope 
in the form of fine prisms collected into spheres. 

3. Damolic Acid. This acid has been least inve?: ligated of all ; 
it is also oily, heavier than w^ater, slightly soluble in it, and 
forms a crystalline barium salt, fusible on being heated, and 
which contains 27*50 per cent, baryta. The damolic acid salt 
crystallizes first out of a solution of damolurate and damolate 
of barium. 



58 ANALYSIS OF THE URmE. 

Detection and Sepabation of these Foue Acids. 
1. Separation of the Acids collectively from tJie Urine. 

Fresh cow urine (80 lbs.) is mixed with calcic hydrate, boiled 
once, drawn off from the excess of lime, and evaporaijed to one- 
eighth. The filtrate is treated with hydrochloric acid after 
being well cooled, and the mother liquid, poured off from the 
hippuric acid, which has sejDarated after twenty-four hours, is 
distilled. By repeated rectification of the milky fluid obtained 
by the first distillation, an oily, faint yellow liquid is finally ob- 
tained, which, for the most part, sinks to the bottom of the water 
in the receiver. In this oil phenylic acid can be readily detected 
by the reaction with ferric chloride, as well as by coloring a 
splinter of pine blue. The amount in human urine is yery 
small.* 

2. Separation of the Acids singly. 

The oil, with the water obtained, according to 1, is treated 
wdth a weighed excess of potassic hydrate, and subjected to 
distillation. A nitrogenous, strongly smelling oil, which has 
not been examined closely, is obtained in the distillate. So 
much sulphuric acid is added to the residue in the retort that 
five-sixths of the potassic hydrate used is saturated, and it is 
then distilled so long as a precipitate is ]3roduced in the dis- 
tillate by basic acetate of lead. By repeated distillation of the 
fluid obtained over common salt, the greatest part of the acids 
are finally obtained in an oily form, and only a very small 
amount of an aqueous solution, with a very strongly acid reac- 
tion, remains. To separate this body with an acid reaction, the 
distillate is saturated with carbonate of sodium, frequently 
shaken, during twelve hours, and the oily layer separated from 
the sodium salt by extracting with ether. 

a. Acids which do not form compounds with carbonate of 
sodium. 

The ether is distilled off from the ethereal solution obtained 
according to 2, and the residue once more subjected to distilla- 
tion with strong potassic hydrate. The potassium compound 

^ Annal. der Chemie u. Pharm., Band 97, p. 134. 



NORMAL CONSTITUENTS OF UBINE, ORGANIC. 59 

wliicli remains beliind is decomposed witli bicarbonate of potas- 
sium, and the distillate obtained completely delijdrated with 
chloride of calcium. By fractional distillation the greatest 
part, which consists of phenylic and taurylic acid, goes over 
between ISO"" and IDS'" C, and they can only be incompletely 
separated further by repeated fractional distillation. The 
chief difference between the two, besides the high boiling point 
of tamylic acid, lies in their behavior with concentrated sul- 
phuric acid, with which taurylic acid unites to form a solid 
compound, and phenylic acid, on the contrar}^, forms a fluid 
compound. 

h. Acids which form compounds with carbonate of sodium. 

The solution of the sodium salt, which was freed from the 
phenylic and taurylic acids by ether, is evaporated, treated 
with sulphuric acid, and distilled. The distillate, which smells 
like butyric acid, separates into an oily and an aqueous layer. 
The whole is boiled with an excess of carbonate of barium, and 
allowed to crystallize. By fractional crystallization different 
barium salts, containing varying amounts of barium, are ob- 
tained (27 to 41 per cent, of barium). That acid is the chief 
constituent whose barium salt contains something over 39 per 
cent, (third, fourth, and fifth crystallization). This acid is the 
damaluric. (See Damaluric Acid.) The second acid, whose 
barium salt contains 27'4 per cent, (first and second crystalliza- 
tion), is damolic acid. (See Damolic Acid.) 

The other btirium salts (evaporated mother-liquor) are mix- 
tures of damoluric acid with another barium salt : whether 
the acid in this salt is butyric, valerianic, or still a new one, 
has not yet been proved. 

In its preparation from human urine, the quantity obtained 
is very small indeed, and if perfectly fresh urine has not been 
taken for the examination, a considerable quantity of acetic is 
always obtained. 

C. Detection of phenol in Jniman iirine. The urine is strongly 
acidulated with tartaric acid, and about one-half of it is distilled 
off on a sand bath. The distillate obtained is shaken twice 
with many times its volume of ether, which extracts the phenol 
present. The phenol which remains behind after distilling off 
the ether is dissolved in a few cubic centimeters of water, and 
this solution is used for the above-mentioned reactions, of 



60 ANALYSIS OF THE UBINE, 

wliicli those of Landolt, Lex, and Plugge are to be especially 
recommended. (Salkowski.) 

Landolt uses the above reaction, precipitation of the phenol 
as tribrom-phenol by bromine water, also for proving its pres- 
ence in normal urine. If human urine (500 cc.) is directly 
treated with an excess of bromine water, it usually becomes 
turbid, and after standing several hours a brownish flocculent 
deposit collects at the bottom of the glass. If this is collected, 
washed, and treated with sodium amalgam, the unmistakable 
odor of phenol is apparent. 

But since bromine water decomposes paraoxybenzoic acid 
with the formation of tribrom-phenol, and salicylic acid with 
bromine water yields dibrom-salicylic acid, which is decom- 
posed by sodium amalgam, and phenol set free, Maly con- 
siders that the behavior of urine with bromine water is not 
sufficient proof of the preexistence of phenol in normal urine. 

According to the above-described procedure of Salkowski, 
phenol was detected after its internal use (0-3 to 0*9 grams 
per day) in every 200 cc. of urine during twenty-two days in 
^\Q patients, and after its external use four times in three 
patients. 

§ 10. Ukinary CoLORiNa Matters. 

I. UHOBTLIN. (M. JAFFE.) 

A. Presence. M. Jaffe ^ found urobilin in normal as well as in 
pathological urine, and also in the bile. This pigment is dis- 
tinguished by characteristic spectroscopic properties, and also 
by the beautiful fluorescence which it shows under certain cer- 
cumstances and by which its preexistence in the urine can be 
readily verified. The high-colored urine of fever patients is 
especially rich in this pigment, but it was also detected in 
forty-five different urines of healthy individuals, so that we may 
well call urobilin a normal constituent of urine. 

B. Separation and Properties. All high-colored urine of fever 
patients shows on spectroscopic examination t with great dis- 

* Archiv flir patliol. Anatomie, Band 47, p. 405. Zeitsclirift fiir analyt. Chem., 
Band 9, p. 150, und Band 3, p. 245. 

f For the method to be used in such examinations, see under the head of 
Blood. 



NORMAL CONSTITUENTS OF URINE, ORGANIC. 61 

tinctuess, frequently only after diluting with water, an absorp- 
tion band, ;/, between tlie Frauenliofer lines b and F, besides 
a characteristic change of color on the addition of alkalies. To 
render the fluorescence ap23arent, as well as to separate the 
pigment from such urines, the following procedure is to be 
adopted. The urine is treated with a not too small excess of 
ammonia, filtered, and the filtrate completely precipitated with 
chloride of zinc solution. The voluminous red or red-brown 
zinc precipitate is washed first with cold and then with hot 
water until the chlorine reaction disappears, it is then boiled 
with alcohol, and finally dried with gentle heat. After pulver- 
izing the mass, it is dissolved in ammonia, and the solution 
precipitated with acetate of lead. The precipitate, which is 
almost always intensely red, is washed with cold water for a 
short time, dried, and then decomposed by alcohol containing 
sulphuric acid. The acid solution of the pigment thus ob- 
tained has the following characteristics : 

1. When concentrated it is brown, when dilute it becomes 
reddish yellow at first, and later rose red, 

2. On spectroscopic examination of the concentrated solution 
the spectrum from the violet end up to about the line b is 
completely dark ; on dilution the darkest part gradually bright- 
ens up, and there finally remains an absorption band, y, with 
indistinct edges between the lines b and F. 

3. On the addition of ammonia the red-yellow or red color of 
the acid solution becomes bright yellow, and finally changes to 
a greenish tinge. The original specimen of urine shows the 
same change of color on the addition of ammonia. 

4. The ammoniacal solution frequently shows a marked green 
fluorescence, which is brought out or strengthened by the addi- 
tion of chloride of zinc. 

5. The alkaline solution of the pigment shows a very char- 
acteristic absorption band, d, between the lines b and F, but 
nearer to b than the band, y, of the acid solution. This band, 
d, is feeble when ammonic hydrate is used, but stronger with 
sodic or potassic hydrate. The ammoniacal solution shows 
the band immediately with great sharpness after the addition 
of chloride of zinc. The band, d^ of the alkaline solution, is 
much more sharply defined and darker than y, and remains 
visible even when extremely dilute. 



62 ANALYSIS OF THE URINE. 

To separate tlie pigment from the acid alcoliolic solution it 
is mixed with about an equal volume of chloroform, and then 
shaken with a great excess of distilled water. The separated 
chloroform is washed once or twice with water, and as soon as 
the wash water begins to be colored the operation is stopped. 
After distilling off the chloroform, an amorphous resinous resi- 
due of a red color remains, which dissolves in alcohol, ether, and 
chloroform, first with a brownish-yellow color, which on dilu- 
tion becomes yellow and finally pale rose color. The solutions 
have a neutral reaction and show a considerable fluorescence. 
They give, examined with the spectroscope, the sharply de- 
fined band, 6, like the alkaline solutions. 

C. Occurrence of Urobilin in Normal Urine. To detect it 100 
to 200 cc. of urine are precipitated with basic acetate of lead, 
and the washed and dried precipitate is decomposed w^ith 
alcohol containing oxalic acid. If this solution still shows no 
absorption bands it is treated with chloroform and shaken with 
water. The urobilin is thus obtained without the application 
of heat, which is to be avoided in concentrated solution, and 
free from those matters which by their absorbing action on the 
blue and violet part of the spectrum destroy the sharpness of 
the band. On the addition of ammonia and chloride of zinc 
the acid alcoholic solution shows exquisite fluorescence, and in 
the spectroscope gives the band, 6, with great sharpness. 

For the preparation of the pure pigment from normal urine, 
the washed and dried lead precipitate from a large amount of 
urine is boiled with alcohol several times, and then decomposed 
with absolute alcohol and sulphuric acid. The solution ob- 
tained is supersaturated with ammonia, the filtrate is diluted 
with about an equal volume of water, and then treated with 
chloride of zinc. A copious precipitate of a brownish-red color 
is produced, while the filtrate remains quite strongly colored, 
but always contains only a small amount of urobilin, though 
large amounts of other urinary jDigments. The chloride of zinc 
precipitate is treated as given above, with fever urine. 

Jaffe further made the interesting observation that freshly 
passed, very pale urine, which showed no trace of an absorption 
band, on standing exposed to the air, often becomes darker, and 
then allows the dark and sharply defined characteristic band of 
urobilin to be recognized in the spectrum. Such urines show, 



NORMAL CONSTITUENTS OF UBINE, ORGANIC. 63 

wlien the band, y, appears distinctly, after the addition of fixed 
alkalies, tlie band, d, also, and ammonia and chloride of zinc oc- 
casion strongly marked flnorescence. Jaffe believes, therefore, 
that a chromogen of the urobilin is to be assumed to exist in 
the original urine, and has convinced himself, by direct experi- 
ments, that this becomes converted into urobilin with its char- 
acteristic qualities by absorbing oxygen. 

We owe to Maly"^ an essential increase of our knowledge of 
the normal urinary pigaient, urobilin. He succeeded in con- 
verting the red coloring matter of the bile, bilirubin, into uro- 
bilin, with all of its characteristic qualities, by the action of 
sodium amalgam. For this purpose pure bilirubin is suspended 
in water, and small pieces of solid sodium amalgam are added 
gradually. If, after a time, the alkaline solution of the bilirubin 
becomes clearer, an excess of the amalgam is added, and if, 
after from two to four days, with frequent shaking, and later, after 
gently heating on the water bath, it becomes no clearer, the 
change is complete. Hydrochloric acid precipitates the color- 
ing matter in the form of dark reddish-brown flakes from the 
fluid decanted from the mercury. The coloring matter, purified 
by repeated solution in alkalies, and j^recipitation with hydro- 
chloric acid, possesses all of the qualities of urobilin. Of these, 
we mention the following : 

1. The urobilin, or, according to Maly, hydrobilirubin, pro- 
duced from bilirubin, does not give Gmelin's reaction for bile 
pigment. 

2. The alkaline solutions vary in color from brown to the yel- 
low of normal urine. The acid solutions vary, according to the 
concentration, from garnet red to brownish red and pale rose 
color. 

3. The spectral absorption between b and F in acid solutions, 
its paling in ammoniacal solutions, and the intense recurrence 
of a dark band removed somewhat to the left, sharply defined 
on the left, rather indistinct on the right, after the addition of 
a small amount of a zinc salt to the ammoniacal solution. 

4. The green fluorescence of the ammoniacal solution con- 
taining zinc, and its disappearance after the addition of an acid. 

5. Its precipitation, by most of the metallic salts, in the 
form of brown or dark red flocculi. 

* Anna!, der Chemie, Band 163, p. 77. 



64 ANALYSIS OF THE URINE. 

In a similar manner biliverclin (the green pigment of bile) 
can be cliangecl into urobilin by sodium amalgam. 

The circulation of these pigments is, therefore, apparent. 
Bilirubin and biliverdin poured into the intestine with the bile, 
change, in their passage to the colon, by absorbing water and 
hydrogen, into urobilin, and, in fact, the coloring matter found 
in the contents of the intestine by Yaulair and Masius, sterco- 
bilin, is, according to the investigations of Jaffe,^ identical with 
urobilin. 

Urobilin is absorbed from the intestine ; it can also easily be 
detected on the way from the intestine to the kidneys in the 
circulation ; at all events, the spectroscopic test was com- 
jDletely successful in the blood serum of the ox. 

When we consider, further, that blood corpuscles in solution 
injected into the veins always cause an icteric urine contain- 
ing bilirubin,'!' then the last link is no longer wanting which 
places in the clearest light the relations between haemoglobin, 
bilirubin, and urobilin.'^: Finally, Hoppe-Seyler § succeeded in 
producing a coloring matter by the action of tin and hydrochlo- 
ric acid on hsematin in alcoholic solution, which in all of its 
properties, chemical as well as optical, completely accorded 
with the urobilin of Jaffe as well as with the hydrobiliru- 
bin which Maly obtained by the action of sodium amalgam 
on bilirubin. Since now the same coloring matter is also pro- 
duced from undecomposed haemoglobin in alcoholic solution 
by tin and hydrochloric acid, there is no more doubt that the 
coloring matter of normal faeces and of the urine must be re- 
garded as a product of the decomposition by reduction of the 
blood pigment, and that the biliary coloring matters, biliru- 
bin and biliverdin, rejDresent intermediate steps of this change, 
or at least stand in near relation to the blood pigment. 

II. UBOCHKOM. (THUDICHUiSI.) 

According to Thudichum, normal urine contains only one 

* Jahresbericlit d. Thiercliemie, Band 1, p. 230. 

f Ktiline, Lelirbucli d. pliysiolog. Cliemie, p. 89, 

:{: Hoppe-Seyler has within a short time given the proof that injections of 
water as well as of a solution of blood pigment into the jugular vein of dogs, 
resulted in a considerable increase of the amount of bile pigment in the bile. 
(Archiv d. Physiologie, Band 9, p. 329.) 

§Bericht d. deutsch. chem. Gesellschaft, Band 7, p. 1065. 



NOBMAL CONSTITUENTS OF URINE, OROANIG. 65 

yellow coloring matter, and the resin of Prout, Scliarling's 
omichmyloxyd, Heller's urrhodin, Schunk's indigrubin, Sclie-, 
rer's urinary coloring matter, also tlie nroligematin of Harley, 
and the substance described by Marcet, are mixtures of the 
products of the decomposition of this yellow pigment, called 
urochrom by Thudichum. Maly's ^ investigations have demon- 
strated, however, that the so-called urochrom, like the coloring 
matters of Scherer, contain considerable quantities of urobilin. 

Thudichum t obtained his urochrom according to different 
methods, of which I give only one here, and in regard to the 
others refer to the original. 

Preparation. The urine is treated with baric hydrate till the 
reaction is alkaline (to one liter of urine about five grams of 
hydrate of barium), and then with a saturated solution of 
acetate of barium. After twelve hours the precipitate is filtered 
off, and the filtrate completely precipitated with acetate of lead 
and ammonia. The washed lead precipitate is triturated in a 
porcelain dish with dilute sulphuric acid, the excess of acid in 
the filtrate saturated with carbonate of barium without the aid 
of heat, the filtrate is made alkaline with baryta water and 
treated with carbonic acid. The filtrate is now precipitated 
with a solution of mercuric acetate, and the precipitate obtained 
washed with cold and hot water. The compound of mercury 
thus obtained must have a yellow color ; if it is gray or dark 
colored the treatment with acetate of lead, etc., must be re- 
peated after decomposing it with sulphuretted hydrogen. The 
coloring matter is obtained by sulphuretted hydrogen in the 
form of a yellow solution from the urochrom-mercuric oxide 
made as pure as possible. This solution always contains in 
addition some hydrochloric or acetic acid. The hydrochloric 
acid can be removed by shaking with freshly precipitated oxide 
of silver, with which, however, a part of the urochrom combines 
to form a voluminous precipitate, while the fluid contains much 
acetate of silver. The yellow alkaline solution is finally freed 
from silver by sulphuretted hydrogen, and the filtrate, after 
evaporation on the water bath, leaves urochrom as an amor- 
phous, solid, yellow substance. 

* Annal. der Cliemie, Band 163, p. 90. 

f Brit. Med. Journ., N. S. 201, p. 509, Nov. 5, 1864. Scliinidt's Jahrbucher, 
1865, Band 125, p. 154. 
5 



66 ANALYSIS OF THE URINE. 

Properties. Urochrom forms yellow scales, wliicli partially 
dissolve in water witli a pure yellow color. It is cliilicultly 
soluble in alcoliol, more easily in ether, very dilute mineral 
acids and alkalies. The aqueous solution becomes darker on 
standing, finally changing to a red color, becoming turbid and 
depositing resinous flocculi. Heat favors the decomposition, 
especially in the presence of acids. Sugar is not formed. Uro- 
chrom is precipitated from the aqueous solution by nitrate of 
silver as a gelatinous mass soluble in nitric acid ; acetate of 
lead gives a white flocculent j^recipitate. Basic acetate of lead 
and mercuric acetate produce a yellow precipitate. Mercuric 
nitrate gives a white precipitate, which on boiling becomes a 
pale flesh-color, while the supernatant fluid is colored rose red. 
By oxidation in the air there is first formed from the urochrom 
a red substance, which corresponds to uroerythrin, and to 
which the red urine of disease owes its color. Under the in- 
fluence of acids, the yellow soluble, as well as the red substance, 
yields three insoluble products, which are deposited from an 
acid solution of urochrom after the addition of water, by suffi- 
ciently long boiling, in brown clumps which collect together in 
balls. On treating this deposit with alcohol, a brown powder 
soluble in potassic hydrate, from which it can be precipitated 
by acetic acid, uromelanin,"^ remains behind. The beautiful 
ruby-red alcoholic solution yields by precipitation with water 
a red resin, which can be decomposed by ether into two bodies. 
The ethereal solution has a very beautiful red color and con- 
tains a resinous acid, omicholic acid, corresponding to the 
omichmyloxide. A yellow substance remains behind insoluble 
in ether, uropittin, which is obtained in the crystalline form 
from absolute alcohol, and on analysis gives the formula 

Uropittin and uromelanin can also be obtained directly from 
the urine. Fresh urine is treated, drop by drop, with concen- 
trated sulphuric acid, and the filtrate evaporated in a retort to 
one-half. After cooling, a black resin separates, from which, 
after washing and drying, uropittin is extracted by alcohol, 
while uromelanin remains behind. 

According to Thudichum, the odor of decomposed acid or 

* Journ. f. pr. Chem., Band 104, p. 257. 



NORMAL CONSTITUENTS OF URINE, ORGANIC. 67 

alkaline urine comes from omicliolic acid and nropittin, or the 
products of their decomposition; it is rendered stronger by 
carbonate of ammonium, but is not caused by it. The urine 
contains, moreover, a volatile ethereal oil, which is colored 
red by boiling with mercuric nitrate, and also cresyl alcohol. 
Urochrom, retained in the blood, is one of the characteristics 
of uraemia ; it is decomposed in the blood to uropittin and 
omicholic acid, which can be recognized again in the tissues, 
in the deposit on the teeth, and in the stinking breath. If the 
coloring matter is retained in the blood, the typhoid symptoms 
of uraemia predominate. Normal urine contains, according to 
Thudichum, no indican ; but this body and the products of its 
decomposition, Avith all of their characteristic properties, have 
been so frequently found in the urine by different investigators, 
that it may well be a question what is normal urine. 

III. imOXANTHm. (HELLER.)— INI^ICAN. (SCHUNCK.) 

Heller calls a substance which occurs in normal urine in small 
amount, in diseased urine, however, in large amount, uroxan- 
thin. It imparts to the urine, when abundant, an intense light- 
yellow color, and possesses the noticeable property of yielding 
by the action of acids, etc., with the separation of a saccharine 
substance, two new pigments, uroglaucin and urrhodin. Ac- 
cording to the investigations of Schunck, Hoppe-Seyler and 
others, this body is nothing else than indican. Hoppe found it 
most abundantly in the urine in carcinoma of the liver, but it is 
also abundant in the urine of dogs. Oscar "Wyss^^ detected 
considerable quantities of indican in the urine first passed after 
an attack of cholera. Jaffa t found a considerable increase of 
indican in the urine after subcutaneous injections of indol, a 
fact which is the more interesting, since, according to Kiihne's 
investigations, indol belongs to the products of pancreatic di- 
gestion in the alimentary canal, and M. Nencki J obtained it 
directly from blood albumen, in considerable quantity, by the 
action of pancreatic ferment. The greatest part of the indol, 
indeed, is passed off with the faeces, and imparts to them their 

* Arcliiv der Heilkunde, Band 9, p. 232. 

f Centralblatt f. d. med. Wissenschaften, 1872, No. 1. 

X Bericht der deutscli. chem. Gesellscliaft, Band 8, p. 336. 



68 AJ^ALYSIS OF THE URINE. 

characteristic odor ; another part is absorbed, and uniting with 
a saccharine substance, is eliminated with the urine as indican. 
If the separation with the excrement is impeded, a greater re- 
sorption may be expected, and, in fact, Jaffe found, in a fatal 
case of incarceration of the small intestine, enormous amounts 
of indican in the urine. 

Eosenstein- found a considerable increase of indican in Ad- 
dison's disease, and Jaffe t found it in all diseased processes 
which cause obstruction of the small intestine. 

This mother substance of indigo is decomposed very readily 
in contact with sul23huric acid, hydrochloric acid, etc. The 
coloring matters, indigo blue, indigo red, etc., separate, while a 
saccharine substance which reduces the oxide of copper, indig- 
glucin, OgHioOg [CjoHioOio], leucin, and volatile fatty acids (acetic 
acid, formic acid, etc.) remain in solution. The same decom- 
position is brought about by ferments, especially by the 
decomposition of the urine ; indigo white is formed, which 
becomes blue when exposed to the air, hence putrefying urine 
frequently shows a bluish-red, metallic, shining pellicle on the 
surface. 

Indican is precipitated from its solution by an ammoniacal 
solution of acetate of lead. 

Preparation, Fresh urine is precipitated with basic acetate of 
lead, filtered and precij)itated with ammonia. The second pre- 
cipitate is filtered off, washed, suspended in alcohol, and de- 
composed by sulphuretted hydrogen. The filtrate is then first 
evaporated at a gentle heat, and finally over sulphuric acid in a 
vacuum. The indican thus obtained is still rendered some- 
what impure by sugar. For its further purification it is dis- 
solved in water, shaken with freshly precipitated hydrated 
oxide of copper, filtered, the filtrate treated with sulphuretted 
hydrogen, precipitated with ether, and the fluid filtered off and 
evaporated best in a vacuum. The indican thus remains behind 
as a clear brown syrup. (Hoppe-Seyler.) 

IV. UROGLAUCIX AND rHEHODIX. — IXDIGO BLUE AND INDIGO RED. 

These substances sometimes occur in the sediment of patho- 

* Vircliow's AtcMv, Band 56, p. 27. 

+ Centralblatt f. d. med. Wissenscliaft., 1872, No. 31. 



XORMAL CONSTITUENTS OF URINE, ORGANIC. 69 

logical urine. They are, as above remarked, according to 
Heller, the products of the oxidation of uroxanthin, according 
to Schunlv they are most probably the products of the decom- 
position of indican. 

a. Urrhodin (indigo red). The ethereal solution after evapo- 
ration leaves the pigment behind in a solid form, but non-crys- 
talline. Indistinct crystals are obtained, however, on very slow 
evaporation of an alcoholic solution. Urrhodin appears crys- 
tallized almost black or in very thin layers carmine red. It 
appears in the form of rose-red granules when amorphous. It 
dissolves in alcohol and ether with a beautiful red color, but is 
insoluble in water. "^ 

After the ingestion of oxindol and dioxindol, these bodies do 
not appear again in the urine of men, dogs or rabbits. Yet 
when the urine was heated with hydrochloric acid and ex- 
tracted with alcohol and ether, red coloring matters were con- 
stantly obtained in small quantity, which had a resemblance to 
those which are obtained by the oxidation of aqueous solutions 
of oxindol and dioxindol in the air. (M. Nencki and Massow.) 
After the internal use of isatin, however, a pigment is obtained 
both from dog and human urine, which corresponded with a 
pigment, which Nencki t obtained from the urine of a woman 
suffering from paralysis of the cervical part of the spinal cord, 
and which appears to be identical with indigo red (urrhodin). 

b. Uroglaucin (indigo blue). Uroglaucin appears as a blue 
powder which consists of microscopic needles terminating in a 
fine point, but which seldom occur isolated, being usually col- 
lected together in groups of two, three, or several. They fre- 
quently form star or circular-shaped groups, which are again 
joined together and present large clumps of radiating bodies. 
Indigo blue is capable of sublimation, and can be reduced by 
sulphate of iron, etc. It is often found in the urine in degene- 
ration of the kidney, and at times, according to Yirchow, in the 
crystalline. form. In putrefying urine it occurs as a product of 
the decomposition of indican. Such a urine frequently becomes 
blue on shaking with air, and on standing a blue iridescent 
pellicle forms on the surface, in which, at times, microscopic 



* Heller's Arcliiv, 1846, p. 31. 

f Eericbte d. deutsch. cliem. Gcsellscliaft, Band 7, p. 1593. 



70 ANALYSIS OF THE URINE. 

needles of indigo can be recognized. (Hoppe-Seyler.) The ad- 
dition of hydrochloric or nitric acid frequently separates it from 
the urine mixed with uric acid as a precipitate, which is gradu- 
ally deposited. 

These products of the decomposition of indican can be 
obtained from the urine by different methods. 

A. Fi-ejoaration by the method of Schunck. The urine is 
treated with basic acetate of lead as long as a precipitate occurs, 
filtered, and the filtrate precipitated with an excess of ammonia, 
by which the indican (uroxanthin) is precipitated in combina- 
tion with oxide of lead. The precipitate, collected and washed, 
is decomposed completely by cold dilute hydrochloric or sul- 
phuric acid, and the solution is filtered. If there is much indigo- 
forming material present, the filter and precipitate, and also 
the surface of the brown filtrate, are colored with a blue sub- 
stance ; if there is but little present, the blue pellicle is formed 
only after twenty-four or forty-eight hours on the filter, never 
later. The brown filtrate, after removal of the indigo blue, 
which gradually separates, dejDosits on boiling a dark brown 
powder, which has the same appearance as that which can be 
obtained directly from the extractive matter of the urine by 
boiling it with acids, and which partly dissolves in sodic 
hydrate with a brown color and partly remains undissolved. 
The undissolved portion is separated into two bodies by boil- 
ing alcohol, one of which dissolves in it with a purple-blue 
color, and appears to be identical with indigo red, the other 
has the characteristics of indigo blue.^ 

B. Preparation by the method of Kletzinsky and Keller. 
Urine, which is colored blue by mixing with fuming hydro- 
chloric acid, is completely precipitated by basic acetate of lead, 
and the filtrate, freed from the excess of oxide of lead by sul- 
23huretted hydrogen, is evaporated to one-third. The fluid, while 
still warm, is allowed to flow into two or three times its volume 
of fuming hydrochloric acid, and allowed to stand a few days, 
during which time a thin, coppery-red, iridescent pellicle forms 
on the surface of the mixture, and the fluid gradually becomes 
cloudy. It is filtered, the bluish-black mass which is separated 
is washed completely with water, and treated with ether after 

* Journ. f . pr. Chem., Band 75, p. 378. 



NORMAL CONSTITUENTS OF URINE, ORGANIC. 71 

drying over sulpliuric acid ; tlie etlier becomes dark red or 
purple, and contains a red, amorphous, resinous mass, urrliodin 
(indigrubin, according to Scliunck). Tlie residue left by the 
ether is then boiled with alcohol, and the deep bottle-blue 
solution is left to itself in closed flasks. After some months a 
velvet-black sediment has dej)Osited, which frequently contains 
rudimentary crystals (the elementary analysis of this precipi- 
tate corresponds, according to Kletzinsky, with that of indigo 
blue). In urine which is very rich in indican there is no need, 
according to my experience, of this detailed manipulation ; 
such a urine, on mixing an equal volume of hydrochloric acid, 
very soon deposits the pigments. The amount obtained is 
always very small, and with less than ten to twenty pounds of 
urine the work should not be undertaken. 

C. Detection. — 1. The following very pretty reaction of Heller 
serves for the detection of even small amounts of indican. Three 
to four cc. of strong fuming hydrochloric acid are mixed in a 
test tube with thirty or forty drops of the urine to be tested, or 
the urine, after the addition of a little hydrochloric or nitric 
acid, is heated to boiling. If indican is present the mixture is 
colored from a reddish violet to intense blue by the decomposi- 
tion of this body. If with small amounts of indican the reaction 
fails, it can be made far more delicate by the addition of two 
or three drops of strong nitric acid. There results from this 
refinement of the test, not immediately but in a few minutes, a 
beautiful violet color, which first plays rather into blue, but 
later rather into red, and sooner or later becomes dirty red, and 
at last yellow again. The color appears almost always with- 
out the addition of nitric acid, but the latter enables us to de- 
tect the least traces of indican. Indican suffers in this reaction 
as in the others a decomposition into indigo blue, indigo red, 
and sugar. 

2. Ten cc. of the urine to be tested for indican are treated 
with an equal volume of hydrochloric acid, and then a saturated 
solution of calcic hypochlorite is added drop by drop. The 
mixture becomes, according to the amount of indican present, 
red, violet, green, or blue, but after filtering, under all circum- 
stances, it leaves behind on the filter a distinct blue tinge. 
(Jaffe.)^ 

* Arcliiv der Physiolog. , Band 3, p. 448. 



72 AI^ALYSIS OF THE UBINE. 

3. According to Stockvis the urine to be tested should be 
warmed with two parts of impure nitric acid to 60° or 70° and 
shaken with chloroform or ether. Both solutions are then 
quickly colored violet blue, and show, when placed before the 
slit of the spectroscope, the characteristic absorption bands of 
indigo blue between C and D. 

The solutions of sulphindigotic acid give, on spectroscopic 
examination, a sharp, dark absorption band between the lines 
C and D, which reaches beyond D when the solution is more 
concentrated. 

I have had an opportunity here to observe a urine very rich 
in indican, for a long period. It was secreted at different times, 
and for a long period uninterruptedly by a young man eighteen 
to twenty years of age of apparently healthy constitution. 

This urine, treated with about an equal amount of hydro- 
chloric or nitric acid, soon became violet, then darker, and at 
last a deep, dark blue. After shaking and standing awhile the 
pigment separated either as a deep blue scum or as a thin, red- 
dish-blue, iridescent pellicle. 

The washed coloring matter consisted of a deep blue powder 
with a copper-red streak, which dissolved in boiling alcohol, 
but on cooling separated, for the most part, again, while the 
supernatant fluid remained colored violet or reddish (urrhodin). 

The product thus obtained could be sublimed at a moderate 
heat, when it first gave rise to beautiful red fumes, and then 
was deposited as a reddish-brown sublimate. Seen under the 
microscope it shows the above-mentioned groups of needles. 
This sublimate could not be distinguished from sublimed in- 
digo, and also its behavior to concentrated sulphuric acid, nitric 
acid, and especially reducing agents, such as ferrous oxide, sul- 
phide of ammonium, etc., completely corresponded with that 
of indigo.^ 

The pigment was entirely destroyed by evaporating the urine, 
so that it was no longer capable of demonstration in the resi- 
due. Nitrous acid destroyed it also. 

It remains for me to call attention to a peculiar behavior of 
this urine toward concentrated sulphuric acid : if a small amount 
of it was treated wdth a sixth or a fourth of its volume of con- 

* Annal. d. Cliem. u. Pharm., Band 90, p. 120. 



NORMAL CONSTITUENTS OF URINE, ORGANIC. 73 

centrated sulphuric acid, without mixing, there occurred, first, 
at the point of contact of the two fluids, a red coloration, which 
always became darker, the color finally spread through the 
whole mass, and the fluid became a deep, dark red, which 
changed to a purple yiolet. This play of colors was perfectly 
similar to that which jaundiced urine yields on treating with 
sugar and sulphuric acid ; yet here the color appeared without 
the addition of sugar, and failed to appear when the pigment 
was decomposed by evaporation. 

Although indican occurs very frequently in normal urine, at 
least in small amount, 3'et it is not improbable that it can be 
increased, in certain diseases, so as to form a symptom of the 
disease, and, therefore, it well deserves the attention of physi- 
cians. At all events it is of great interest to recognize indican, 
that is, indigo blue, etc., as a probable product of the decom- 
position of protein matters, which is rendered more likely by 
the fact that the products of decomposition of indican include 
among others, as above remarked, in addition to a saccharine 
substance, both leucin and volatile fatty acids. 

Kelatively very large amounts of indigo are obtained from 
the urine of the horse and cow. Creasote and oil of bitter 
almonds, even taken in small doses, are said to increase the 
amount of indigo in the urine very much. (Kletzinsky.) 

It is readily seen that by the combination of urobilin with 
varying amounts of urrhodin and uroglaucin, very manifold 
shades of color in the urine (greenish, grass green, violet, red- 
dish) can result. 

v. UROEBYTHRIN. 

That coloring matter is called uroerythrin which imparts to 
sediments of uric acid and urates their brick-red or rose-red 
color, and which, on contact with the air, increases considerably. 
Uroerythrin is said also to occur in solution in pathological 
urine, to which it imparts a red color. According to Thudi- 
chum, it probably is the result of the oxidation of normal 
urochrom. 

The red sediments which occur so frequently appear, how- 
ever, to contain at least two different pigments, since according 
to Hoppe many sediments yield to chloroform a beautiful pur- 



74 AI^\4.LTSIS OF THE TIBINE. 

plisli-red pigment soluble in alcohol, while according to Heller 
iiroerythrin is insoluble in alcohol. According to Heller, alco- 
hol only extracts from the sediments urrhodin (indigo red) and 
urogiaucin (indigo). According to Jaffe, urobilin (see above) 
is not identical with the pigment of these sediments. Even if 
in many sediments urobilin undoubtedly occurs, it aj)pears to 
be comjDletely wanting in others, or to exist in common with 
one or several other pigments by which its entire demeanor is 
altered. 

VI. BLACK UEINE. 

J. Yogel found a dark-colored urine after breathing arseni- 
uretted hydrogen. Waldenstrom, Almen, Salkowski, Bartels,^ 
and others observed after inunctions of tar, but especially after 
the external as well as internal use of carbolic acid, tarry-look- 
ing, almost black urine. According to Waldenstrom, Salkowski, 
and AlmeUjt carbolic acid can be detected in the urine in the 
latter case. 

MalyJ did not succeed, however, in such cases in detecting 
phenol in the distillate. The dark color spoken of does not 
seem to occur in the bladder, but first appears on exj)osure to 
the air. According to the observations of Maly, the brown- 
ing or blackening first appears as a zone in the upper layer of 
fluid, which gradually descends from above downward, when 
the urine remains at rest. 



§ 11. Keyptophanic Acid. 

According to the investigations of Thudichum,§ kryptophanic 
acid discovered by him is the normal free acid of the urine. 
(?) It forms the chief mass of the so-called extractive matter, and is 
obtained from normal urine in the following manner : 

The urine is made alkaline with milk of line, filtered, evajDO- 
rated, then acidulated with acetic acid and concentrated until 
the salts, etc., crystallize out. The syrup decanted from the 

* Oral communication. 

f Neue?5 Jalirb. f. Pharm., Band 34, p. 112. 

I Jaliresbeiiclit u. d. Fortschritte der TMercliemie, 1871, p. 184. 
§ Centralbl. f . d. med. Wissenscliaft.,18T0, p. 195 and 209. Zeitschr. f. analyt. 
Chemie, Baiid 10, Heft 1 . 



NORMAL CONSTITUENTS OF URINE, ORGANIC. 75 

crystals is shaken in a flask witli five times its volume of 90 
per cent, alcohol, when impure krytophanate of calcium sepa- 
rates, which is repeatedly washed with alcohol. To purify it^ 
the crude calcium salt is dissolved in water, and precij)itated 
with a large excess of a saturated solution of acetate of lead. It 
is filtered and five or six times its volume of strong alcohol is 
added to the filtrate, by which white neutral krytophanate of 
lead is precipitated. The precipitate is collected on a filter, 
washed with alcohol, then with a little water, and lastly with 
ether ; it is dried in a vacuum and finally decomposed with a 
sufficient amount of sulphuric acid. For its further purifica- 
tion the acid is saturated with baryta water, the excess of ba- 
rium is removed by carbonic acid, the krytophanate of barium 
precipitated with alcohol, again dissolved in water and once 
more precipitated with acetate of lead in excess. The filtrate 
which now results yields, after the addition of alcohol, pure, 
white, neutral krytophanate of lead. To obtain the free acid 
the lead salt is decomposed with sulphuric acid. 

The product thus obtained is amorphous, gummy, transpa- 
rent, soluble in water, less so in alcohol, and least in ether. 

Thudichum attributes to his new, long-hidden acid a great 
physiological as well as pathological significance, but further 
investigations must yet decide whether this is really a pure 
substance, which from the mode of preparation is somewhat 
doubtfuL 

J. Pircher^ and A. Silversidget could not convince them- 
selves of the existence of kryptophanic acid. Both investiga- 
tors arrived at no decisive result. Hlasiwetz and Habermann, % 
however, suppose that Thudichum's kryptophanic acid is only 
an impure glutamic acid, which also, like kry]Dtophanic acid, 
reduces cupric oxide in alkaline solution, and whose formula 
(€5119^04) corresponds with that of kryptophanic acid (tVHgNO,) 
within one atom of oxygen. Further investigations upon this 
substance are, therefore, very much to be desired ; certainly 
the occurrence in the urine of glutamic acid, an interesting pro- 
duct of the decomposition of animal as well as vegetable albu- 
minoid bodies, would be of great physiological interest. 

* Centralblatt f. d. med. Wissenschaft.,1871, No. 4. 
f Journ. of Anat. and Plijsiol., vol. vi., p. 422. 
J Annal. d. Cliem. u. Pharm., Band 159, p. 150. 



76 AI^ALYSIS OF THE TJIilNE. 

B. Inorganic, 
§12. 

The urine contains of tlie inorganic bases especially sodium, 
potassium, calcium, and magnesium, partly combined, espe- 
cially the first two, with uric and hippuric acids, but also wdth 
sulphuric, j)hosphoric, hydrochloric, and nitric acids. Besides 
these, small amounts of iron and silicic acid, finally also am- 
monium salts, especially in alkaline urine. The urine does not 
contain free gases except carbonic acid, nitrogen, and traces of 
oxygen ; pathologically, however, sulphuretted hydrogen some- 
times occurs. The whole amount of non-volatile salts con- 
tained in the urine differs in different persons and under dif- 
ferent pathological conditions very much. Thus in men varia- 
tions of from 9*06 to 24*50 grams occur, in women from 10*28 
to 19*63 grams. Lehmann found in his own urine daily, while 
on a mixed diet, 15*245 grams (varying between 9*652 and 17*284 
grams).* ^ 

§ 13. Chloride of Sodium. 

A. Presence. We may assume that almost all of the chlorine 
occurring in urine is in combination with sodium. The amount 
of chloride of sodium secreted varies in different persons and 
at different times of the day. 

Hegar has communicated observations on the variations in 
the amount of chloride of sodium in eight persons, the results 
of which are briefly as follows : On an average the chlorine 
separated in twenty-four hours amounted to 10*46 grams, cor- 
responding to 17*5 grams of chloride of sodium. The secre- 
tion of chlorine is the greatest in the afternoon ; at night, how- 
ever, it diminishes considerably and rises again in the morning. 
Physical exercise increases, and slight disturbance of the health 
diminishes the secretion quite rapidly. The amount is rapidly 

" E. Weidner. Investigations of normal and pathological urine, especially in 
regard to tlie proportion of lime, magnesia, potassium, sodium and iron to the 
other constituents of the urine. Rostock bei Adler's Erben, 18G7. E. Salkow- 
ski, investigations concerning the secretion of the alkaline salts. Virchow's 
Archiv, Band 53, p. 303. 



NORMAL CONSTITUENTS OF URINE, INORGANIC. 77 

increased by drinking water, "but it diminislies later so mucli tlie 
more. After taking beer the amount of clilorine is unusually 
small. With regard to the whole amount of chloride of sodium 
separated in twenty-four hours, the observations of Bischoff " 
diifer somewhat from the statement of Hegar. He found in 
his own urine, in twenty-four hours, between 8 '64 and 24*48 
grams, and gives as the average 14*73 grams. 

The amount of cloride of sodium is extraordinarily diminished 
in many diseases, indeed, in all in which abundant exudations 
take place from the blood. Eedtenbacher saw in inflammations 
of the lungs the amount of chlorine often diminished to a mini- 
mum, so that in some cases no cloudiness at all could be ob- 
served after adding nitrate of silver. 

B. Microscopic Properties. Chloride of sodium crystallizes 
under the microscope in extraordinarily beautiful, regular, 
stair-like cubes. It suffers a peculiar modification when it 
crystallizes from a solution which contains urea at the same 
time ; the ordinary cubes are thereby changed into octahedral 
and tetrahedral forms. 

C. Chemical Properties. — 1. If water is poured over pure, 
coarsely crushed, crystalline rock-salt, and the fluid, after a 
thorough shaking, is allowed to stand twenty-four hours at 12° 
to 50° C, an invariable amount of salt is dissolved. In 10 
cc. of this clear filtered solution Liebig and others found, as 
an average of many very nearly coinciding estimations, 3*184 
grams of common salt. 

2. Nitrate of silver produces, in all fluids which contain chlo- 
ride of sodium, a white caseous precipitate of chloride of silver, 
insoluble in nitric and hydrochloric acids. If the urine, how- 
ever, after it has been acidulated with nitric acid, is treated 
with a solution of nitrate of silver, the precipitate which 
results is never pure chloride of silver, but the pigments, 
uric acid, etc., are also precipitated by the silver salt, and in 
the quantitative estimation of chlorine by nitrate of silver this 
is not to be disregarded. 

3. If a concentrated solution of chloride of sodium is mixed 
with a concentrated solution of mercuric nitrate, the two salts 
quickly undergo mutual decomposition, nitrate of sodium is 



* Bischoff, Urea, 1853, p. 33. 



78 ANALYSIS OF THE URINE. 

formed, and the fluid solidifies to a crystalline mass of corrosive 
sublimate. Tlie same decomposition takes place in dilute solu- 
tions also, only tlie corrosive sublimate formed does not sepa- 
rate, but remains in solution in tlie fluid. 

We liave seen under urea, that in a solution of this sub- 
stance, which is feebly acid or neutral, mercuric nitrate pro- 
duces a precipitate of urea with mercuric oxide. Corrosive 
sublimate, on the contrary, produces no precipitate in acid or 
neutral solutions of urea. After this premise it will be easy 
to understand the following reaction, which Liebig has made 
use of for the quantitative estimation of chloride of sodium in 
the urine. If the phosphoric and sulphuric acids are removed 
from specimens of urine by the addition of nitrate and hydrate 
of barium, and if the alkaline filtrate is made neutral again or 
feebly acid by nitric acid, the fluid is a weak acid solution of 
chloride of sodium with urea. *If now we treat this Avith a 
dilute solution of mercuric nitrate, drop by drop, a white pre- 
cipitate will occur at the point of contact of the two fluids, 
which, however, disappears again on stirring the mixture. The 
precipitate which first takes place is the compound of urea- 
mercuric oxide. But, since chloride of sodium is in the fluid, 
the mercuric nitrate is immediately changed to corrosive subli- 
mate, which, as is knoAvn, does not precipitate urea in feebly 
acid solutions. Therefore, the precipitate which first occurs 
disappears, and the fluid becomes a^ clear as before. This play 
of reactions is repeated in the same way until all of the chlo- 
ride of sodium present has been used up in changing the 
mercuric nitrate into corrosive sublimate. At last it ceases, 
another drop of the mercuric nitrate solution finds no more 
chloride of sodium by which it can be changed into corrosive 
sublimate, and a permanent precipitate of urea-mercuric oxide 
is produced. If the amount of the mercuric nitrate solution 
which has been added up to this point is known, the amount 
of chloride of sodium w^liich was present can be readily reck- 
oned, since one equivalent of mercuric oxide corresponds to 
just one equivalent of chloride of sodium. 

4. If a neutral solution of chloride of sodium, which at the same 
time contains phosphate of sodium, is treated with a feAV drops 
of a neutral solution of chromate of potassium, and a solution 
of nitrate of silver is allowed to flow into it, drop by drop, from 



NORMAL CONSTITUENTS OF URINE, INORGANIC. 79 

a pipette, all of tlie clilorine will be first precipitated as chlo- 
ride of silver. When this point has been reached, the next 
drop of the silver solution gives a permanent red color, due to 
chromate of silver. The phosphoric acid remains completely 
in solution up to this point, since the silver salt precipitates 
these three acids in the following succession : chlorine, chromic 
acid, phosphoric acid. (Mohr's volumetric method.) 

D. Detection. The reaction with nitrate of silver already 
given always serves for the recognition of chloride of sodium 
in the urine. But the urine contains phosphoric acid, and this 
also gives, with oxide of silver, a precipitate of phosphate of 
silver, which, however, is soluble in nitric acid, while chloride 
of silver is not soluble in this reagent. We must, therefore, in 
testing urine for chlorine, add to it, either before or after the 
addition of the silver solution, nitric acid enough to give a 
strong acid reaction. In the first case the phosphate of silver 
will not then be precipitated, but in the second it will dissolve 
again directly, and only the choride of silver remains in caseous 
flakes. 

If the urine is evaporated to a syrupy consistence, the chlo- 
ride of sodium crystallizes out after a time in cubes or octa- 
hedra, which can easily be recognized. The spectroscopic test, 
obtaining the yellow sodium flame, serves for the direct recog- 
nition of the sodium. 

§ 14 Chloeide of Potassium. 

The urine, together with chloride of sodium, contains chlo- 
ride of potassium, which has the same crystalline form as chlo- 
ride of sodium. To detect the potassium in urine it is treated 
with a little hydrochloric acid, an equal volume of a mixture of 
alcohol and ether is added, and afterward a solution of chlo- 
ride of platinum. After a few hours the potassio - platinic 
chloride, mixed with ammonio-platinic chloride, will have sep- 
arated in beautiful octahedra, which are readily recognizable 
under the microscope. 

Tartaric acid can also be used with advantage. 100 to 150 
cc. are evaporated to one-eighth of the original volume, allowed 
to cool, filtered, and the filtrate treated with a concentrated 
solution of tartaric acid in excess. After standing ten hours in 



80 Aj}^ALY8IS of THE TTEINE. 

a cool place tlie separation of acid tartrate of potassium is com- 
plete. Salkowski " obtained by this method from 500 cc. of 
urine 2*7 to 3 grams of cream of tartar. 

"Weidner t found in his own urine, on an average, 3-91 grams 
of j)otassium in twenty-four hours. The maximum amounted 
to 5*9 grams, the minimum 2 grams. The relative proportion 
of potassium and sodium was 1 : 1'35. :|: 

§ 15. Sulphates. 

A. Presence. Many experiments have been undertaken, under 
the direction of Yogel, concerning the amount of sulphates in 
the urine. From these determinations it has been proved that 
an adult passes, on an average, 2*094 grams of sulphuric acid in 
twenty-four hours, which coincides with the more recent inves- 
tigations of Weidner, who found on the average 2"1 grams. 

During the time of digestion the amount of sulphuric acid 
secreted increases, it sinks somewhat in the night, and reaches 
its minimum in the forenoon hours. The secretion increases 
for a short time on copious drinking of water, but later decreases 
all the more. (Gruner.) Sulphates taken into the economy are 
comj^letely separated again with the urine in from eighteen to 
twenty-four hours. Pure sulphur also increases the amount of 
suljDhuric acid in the urine. Without doubt the sulphur of the 
protein substances ingested with the food is gradually oxidized 
to sulphuric acid in the blood, and is then eliminated with the 
urine, combined with alkalies. Therefore, after an abundant 
meat diet, not only the urea, but also the sulphuric acid is found 
increased in the urine. Disease, also, frequently exercises a 
decided influence on the excretion of sulphuric acid, so that it 
is often increased and often diminished. 

B. Chemical Properties. Some of the sulphates are soluble in 
water, and some insoluble. The sulphates of the alkalies and 
alkaline earths are not decomposed by a red heat; if, however, 
they are heated with charcoal or organic matters which yield 
charcoal on being heated, they undergo a reduction to free sul- 

* Archiv d. Physiologie, Band 2, Heft 351. f Loc. cit. 

X Investigations of the secretion of alkaline salts by E. Salkowski, Vircliow's 
ArcMv, Band 53. 



NORMAL CONSTITUENTS OF URINE, INORGANIC. 81 

pliur, wliich can be recognized by the odor of sulphuretted hy- 
drogen, if the red-hot mass is moistened with a little acid. If 
this test is made on polished silver a black spot is produced. 

1. Chloride of barium produces, in solutions of the sulphates, 
a white, fine pulverulent precipitate of sulphate of barium, in- 
soluble in nitric and hydrochloric acids. 

2. Acetate of lead precipitates sulphate of lead. 

3. If organic matter and sulphates are moistened and exposed 
to a tolerably high temperature, sulphuretted hydrogen is 
formed. It is possible that the sulphuretted hydrogen, at times 
occurring in the urine, is formed in this manner. 

C. Detection. Sulphuric acid gives, with barium salts, a pre- 
cipitate insoluble in acids, and apparent, even when very dilute ; 
in testing a urine for sulphuric acid, therefore, we make it 
strongly acid with nitric or hydrochloric acids, for the reasons 
given under chloride of sodium, and then treat it with a solu- 
tion of chloride or nitrate of barium; any precipitate wliich 
takes place (sulphate of barium) points with certainty to the 
presence of sulphuric acid. 

§ 16. Acid Phosphate of SoDroM. 

A. Presence. This salt, according to Liebig's investigations, 
without doubt occurs in the urine, and is also in most cases 
the chief cause of its acid reaction. 

Many determinations of the amount of phosphoric acid in 
the urine have been made by Breed.^' The average excretion 
of phosphoric acid in twenty-four hours in a number of per- 
sons was from 3 "765 grams to 5 '180 grams. This daily amount 
of phosphoric acid, however, appears to me to be somewhat 
too high according to the numerous determinations given in 
recent times, which is to be attributed to the very defective 
method of determination with ferric chloride, which has hither- 
to been used. According to the volumetric method with oxide 
of uranium solution, first proposed by me for the determination 
of the phosphoric acid in the urine, I have seldom found more 
than two grams of phosphoric acid in twenty-four hours under 
normal conditions. Weidner found the maximum was 3 '8, the 

*Ann. d. Chem. u. Pliarni., Band 78, p. 150. 



82 ANALYSIS OF THE URINE. 

minimum 2*25, and tlie average 2 '76 grams. Increased drink- 
ing augments the secretion a little, yet, according to Winter, 
only during the first three or four hours. Winter also found 
that at night considerably more phosphoric acid is secreted 
than in the morning, but most of all at midday, and both 
Winter and Breed observed that the amount of phosphoric acid 
very considerably increased after taking food. The variations 
in disease are tolerably great, as is readily understood ; accord- 
ing to Heller, it should keep tolerable pace with the sulphates.* 
B. Chemical Properties. — 1. The acid phosphate of sodium is 
readily soluble in water and gives to it an acid reaction. On 
heating it to a red heat alone it is not decomposed, but if it is 
at first very intimately mixed with charcoal, or ignited with 
organic matters, a part of the phosphoric acid is reduced, and 
phosphorus is formed which is immediately volatilized. 

2. Chloride and nitrate of barium give in solutions of phos- 
phate of sodium a precipitate of phosphate of barium, which 
is readily soluble in acids. 

3. Phosphoric acid forms compounds with calcium and mag- 
nesium which are insoluble in water, but are soluble even 
in acetic acid without decomposition. In the urine we find 
phosphate of calcium and phosphate of magnesium, which are 
held in solution by the free acids or acid salts. If we neutralize 
the urine with ammonia, the phosphate of calcium is precipi- 
tated unchanged, the phosphate of magnesium, however, takes 
up ammonium and appears as ammonio-magnesian phosphate 
in the precipitate. 

The formation of these compounds, which occur in alkaline 
urine as a sediment, depends on this. The alkaline reaction of 
a urine comes mostly from carbonate of ammonium produced by 
the decomposition of urea ; but as soon as this has formed the 
free acid of the urine disappears, and the earthy phosphates can 
no longer be held in solution. The phosphate of calcium then 
separates usually in the amorphous form, but the phosphate of 
magnesium separates in beautiful crystals as ammonio-magne- 
sian phosphate. 

4. Ferric chloride gives, in solutions of the phosphates which 
are acidulated with free acetic acid, a yellowish-white, gela- 

* See Weidner, loc. cit. 



i 



JSrORMAL CONSTITUENTS OF URINE, INORGANIC, 83 

tinons precipitate of phosphate of iron. This compound is 
soluble in all acids except acetic, therefore a solution from 
which we wish to pecipitate the phosphoric acid by ferric 
chloride must contain no other free acid. If, however, any 
other free acid is present, acetate of sodium and free acetic acid 
are added to the fluid before the precipitation with ferric chlo- 
ride ; in this way the solution is rendered acid with acetic acid, 
in which the phosphate of iron is insoluble. 

5. If a phosphate is dissolved in water or acetic acid and 
treated with acetate or nitrate of uranium, a yellow precipitate 
of phosphate of uranium immediately takes place. The pre- 
cipitate does not dissolve in water and acetic acid, but does in 
the mineral acids, from which it may again be completely pre- 
cipitated by a sufficient excess of alkaline acetates and heat. 
We make use of this reaction for the volumetric estimation of 
phosphoric acid. 

C. Detection. (See § 17.) 

§ 17. Phosphates of Calcium and Magnesium. 

As above remarked, these two earthy phosphates are in solu- 
tion in acid urine, but they are separated from it as soon as it 
is rendered alkaline. A long series of observations, which I 
commenced on the secretion of the earthy phosphates in four 
healthy young men, gave the following results : 

1. In the normal condition there was passed by an adult 
male from twenty to twenty-five years of age, on a mixed diet, 
in twenty-four hours, as a mean of fifty-two observations, 0.9441 
to 1"012 grams of earthy phosphates. 

The maximum amounted on the average to from 1'138 to 
1*263 grams ; only once was 1*554 grams passed in twenty-four 
hours. 

The minimum amounted to an average of 0*8 gram, and once 
only 0*328 gram was passed. 

2. The phosphate of calcium amounted on an average of fifty- 
two estimates to from 0*31 to 0*37 gram. The maximum aver- 
aged 0*39 to 0*52 gram ; only once was 0*616 gram passed. 

The minimum was tolerably' constant at 0*25 gram ; once only 
it amounted to 0*15 gram. 

3. The phosphate of magnesium amounted on an average 



84 ANALYSIS OF THE URINE. 

of fifty-two observations to 0*64 gram. The maximum aver- 
aged 0*77 ; only once 0'938 gram was passed. The minimum 
amounted in the average to 0*5, but sank once to 0'178 gram. 

4. In the normal condition on the average about one equiva- 
lent of 3CaO,P05 to three equivalents of 2MgO,P05 is passed. 
In one hundred parts of earthy phosphates 67 per cent, consist 
of phosphate of magnesium, and 33 per cent, of phosphate of 
calcium. 

5. Calcium salts ingested do not pass out in the urine, or 
only in very small amount ; the whole amount of phosphates 
secreted normally does not thereby suffer any very great in- 
crease. 

6. In disease the absolute amount of earthy phosphates, as 
well as the relative proportion between calcic and magnesic 
phosphates, departs much from the normal secretion. 

Detection. The recognition of phosphoric acid in acid urine 
presents no difficulties ; the precipitate Avhich takes place im- 
mediately upon the addition of ammonia, and consists of earthy 
phosphates, leaves no doubt of its presence. It can readily 
be determined if the urine contains any more phosphoric acid 
than was precipitated with the calcium and magnesium, by 
filtering off the ammonia precipitate, and testing the filtrate 
acidified with acetic acid with uranium solution ; the formation 
of a yellowish-white precij^itate wdll show the amount of the 
phosphoric acid which remains. In an alkaline urine we find 
the earthy phosphates in the sediment, and will refer to them 
under that head. If we wish to separate the calcium from the 
magnesium in the precij)itate which takes place on the addition 
of ammonia, and which consists of the phosphate of calcium and 
ammonio-magnesian phosphate, we dissolve the precipitate in 
acetic acid, add a little chloride of ammonium, and then a solu- 
tion of oxalate of ammonium, by which the calcium is precipi- 
tated as oxalate, while the magnesium remains in solution, and 
can be precipitated from the filtrate by the addition of ammonia 
again as ammonio-magnesian phosphate. 

§ 18. Ieon. 

A. Presence. Iron for the most part is found only in very 
minute quantity in the residue of urine after ignition. If a 



NOBMAL CONSTITUENTS OF URINE, INORGANIC. 85 

urine contains blood, iron is more easily detected in tlie 
ash. 

According to the investigations of Magnier ^ the amount of 
iron in a healthy man of medium weight varies between 0*003 
and O'Oll gram in a liter. A mean of fourteen examinations 
gave 0*007 gram of iron to the liter of urine. 

B. Chemical Properties. 

1. Sulphide of ammonium yields in ferrous and ferric solu- 
tions a black precipitate of sulphide of iron, which is readily 
soluble in hydrochloric and nitric acids. 

2. Ferrocyanide of potassium yields in ferric solutions a deep 
blue precipitate of ferrocyanide of iron (Prussian blue). In 
ferrous solutions the precipitate is bluish white, and consists 
of ferricj^anide of potassium and iron. 

3. Sulphocyanide of potassium does not change ferrous solu- 
tions, but it produces the intensely red sulphocyanide of iron 
in ferric solutions. 

4 If a solution of permanganate of potassium is added to an 
acid solution of a ferrous salt, the ferrous oxide becomes con- 
verted into ferric oxide, and when this point is reached, the 
next drop of the permanganate of potassium solution causes a 
beautiful red coloration of the fluid. 

C. Detection. The ash of the residue of urine is always 
chosen for the isolation and detection of iron. It is dissolved 
in a little hydrochloric acid, and the solution divided into two 
parts. The first half is boiled with a drop of nitric acid and 
treated with sulphocyanide of potassium ; if there is the least 
amount of ferric oxide present, the fluid will assume a reddish 
color, which becomes a deep dark red when it is in greater 
amount. "With mere traces of ferric oxide, the color is seen 
most distinctly when the test tube is placed on a white surface 
and examined from above. If, instead of sulphocyanide of 
potassium, ferrocyanide of potassium is added to the second 
portion after boiling with nitric acid and diluting, flocculi of 
Prussian blue separate after standing a time. If the amount 
of iron is more considerable the Prussian blue is immediately 
precipitated. 

" Bericlite d. deutscli. cJbem. Gesellscliaft, Band 7, p. 179G. 



AJVALYSIS OF THE URINE. 



19. Ammonium Salts. 



It is a well-known fact that the detection and estimation of 
the ammonium salts in normal nrine is attended with many 
difficulties. The readiness with whicli the coloring and extrac- 
tive matters decompose, and the urea becomes converted into 
carbonate of ammonium, especially if the above matters are 
present, is well known. This is the reason that we continually 
find different statements concerning the occurrence and amount 
of the ammonium salts in normal urine. If normal acid urine 
is concentrated in a retort at as low a temperature as j)ossible, 
ammonia will always be found in the distillate, while the con- 
centrated urine which remains behind often reddens litmus 
stronger than before. This surprising appearance is exjDlica- 
ble in the following manner : The acid phosphate of sodium 
present in the urine decomposes the urea on the application of 
heat, and ammonio-sodic phosphate is formed. But this salt 
has the property of giving up its ammonia at a temperature 
of 100^, and changing again to acid phosphate of sodium ; the 
acid phosphate of sodium, therefore, acts destructively on the 
urea as long as the evaporation lasts, and the urine can, tliere- 
fore, always retain its acid reaction while a large amount of 
ammonia is in the distillate. 

With some care, however, it is possible to detect with the 
greatest certainty small amounts of ammonium salts in normal 
urine, and the labors of Heintz, Boussingault, and myself re- 
move all doubt on this point. 

O. Schultzen and L. Riess found trimethylamin also in the 
urine in acute atrophy of the liver. 

C. M. Tidy and W. B. Woodmann '^ have carried out thorough 
investigations with regard to the amount of ammonia in the 
urine in health and disease. These authors give as the normal 
average 0*162 gram of NH3 in twenty-four hours. They ob- 
served a diminution to one-half in acute articular rheumatism, 
in albuminuria, phthisis, and nervous diseases. The normal 
amount of ammonia sank to one-quarter in erysipelas, variola, 
typhus and typhoid fevers. It was in normal amount in cancer, 
heart diseases, and chronic alcoholism, and was increased in 

*Proc. of Royal Soc. XX., p. 362. 



NORMAL CONSTITUENTS OF URINE, INORGANIC. 87 

diabetes and gout. It is said to almost wholly disappear from 
the urine shortly before death. In two hundred cases examined 
it was only twice wanting in the urine. 

Hilger found "^ a very considerable increase of ammonia after 
taking asparagus for a long time ; here it is evidently produced 
by the decomposition of the asparagin. 

Detection. To detect ammonium salts in acid urine, freshly- 
passed normal urine is precipitated with a mixture of acetate and 
subacetate of lead, filtered, and the filtrate, while cold, treated 
with milk of lime in a flask. The flask is closed with a stopper 
on which a piece of moistened turmeric paper is fastened, w^hen 
the brown color can be very quickly perceived. Now where 
does the ammonia, set free by milk of lime in the cold, com»e 
from ? Urea is not decomposed by milk of lime in the cold, 
and the coloring and extractive matters are removed by oxide 
of lead. As no substance is discovered, in normal urine ivliich is 
precipitated by the acetate and subacetate of lead, and is decomposed 
by milk of lime in the cold in a few seconds ivith the development of 
ammonia, we must consider the p)re^ence of ammonium salts in nor- 
mal freshly -passed urine as established. 

For my quantitative estimations I used a method given by 
Schlossing, which depends on the fact that an aqueous solution 
containing free ammonia, when exposed to tli9 air at ordinary 
temperatures, allows its ammonia to evaporate in a relatively 
short time, when it is contained in as flat a vessel as jDossible 
in not too deep a layer. The ammonia which escapes is made 
to combine with a standard sulphuric-acid solution and is de- 
termined volumetrically. (See Part Second for description of 
the process.) 

After I had convinced myself of the usefulness and reliability 
of the method,t I commenced the determination of the amount 
of ammonia which is passed by a healthy man in twenty-four 
hours. My experiments showed that in twenty-four hours, on 
an average, 0-7243 gram of ammonia were secreted by a man 
from twenty to thirty-six years of age, which corresponds to 
2-2783 grams of chloride of ammonium. The amount varied in 
twenty-four experiments between 0-3125 and 1-2096 gram of 



* Erlanger Sitzungsbericlite, 1873. 

f Journ. f . pract. Chemie, Band 64, p. 177. 



88 ANALYSIS OF THE URINE. 

ammonia, corresponding to 1*4272 and 3*8038 grams of chloride 
of ammonium. I started my experiments with two healthy 
men of twenty and thirty-six years respectively, and found that 
a somewhat greater amount of ammonia was passed in twenty- 
four hours by the latter on the average. The following sum- 
mary will serve to show the difference : 

Man of 20 years. Man of 36 years. Difference. 



NH3 NH4CI. NH3 NH4CI. NH3 NH4CI. 
In twenty-four hours, 0-G137 1-9305 0-8351 2-6361 0-2214 0-7065 
In 1,000 cc. of urine, 0-3939 12390 05245 1-6560 0*1306 0-4170 

Chloride of ammonium, taken into the economy, passes out 
in part unchanged by the urine. 

§ 20. Silicic Acid. 

Silicic acid occurs only in very small amount in the urine. 
To obtain it the following method is adopted : An amount of 
urine, not too small, is evaporated in a platinum or silver evapo- 
rating dish and ignited. The ash obtained is mixed with an ex- 
cess of a mixture of chemically pure carbonate of sodium and 
potassium, and fused for a time in a platinum crucible. The 
mass is dissolved in water, rendered acid Avith hydrochloric 
acid, and evaporated to dryness in a platinum dish on the water 
bath. The dry residue is extracted with hydrochloric acid and 
water, and pure silicic acid remains behind. 

The silicic acid thus obtained is Avhite, pulverulent, without 
taste or odor, and grits between the teeth. It is soluble neither 
in w^ater nor in acids, but boiled with a solution of carbonate of 
sodium it is taken up entirely without leaving any residue. 
(Tests of purity.) 

§ 21. Nitrates and Nitrites. 

According to the investigations of Schonbein, every normal 
urine contains small amounts of nitrates, which without doubt 
come from the food taken, since all spring and river water, as 
well as many vegetables, cabbage, spinach, salad, etc., contain 
small amounts of nitrates. The nitrates are gradually reduced 
to nitrites by the urinary fermentation which soon takes place 



NORMAL CONSTITUENTS OF TIBINE, INORGANIC. 89 

on standing, and tliey appear to suffer a further decomposition 
in the later stages of fermentation. The following are to be 
mentioned as delicate reagents for nitrous acid : 

1. A deep blue color is produced by the slightest amount of 
nitrites with a paste of starch and iodide of potassium feebly 
acidified with dilute sulphuric acid. 

2. An acidulated solution of pyrogallic acid is colored deep 
blue by nitrites with the evolution of nitric oxide gas. If the 
test is performed in a flask, the nitric oxide gas on contact with 
the air becomes nitric peroxide, which turns a strip of paper 
moistened with starch and iodide of potassium paste, and hung 
in the flask, blue, and decolorizes indigo paper. 

As long as the urine is completely clear, it never shows the re- 
actions given for nitrous acid ; if, however, a cloudiness appears, 
due to commencing fermentation, the formation of nitrous acid 
immediately takes place, and the urine now shows an evident re- 
action with sulphuric acid and iodide of potassium, and starch 
paste. Also an indigo solution acidulated with hydrochloric 
acid and then completely decolorized by adding a few drops of 
potassic pentasulphide (Mehrfachschwefelkalium) is made blue 
again directly by such a urine. (Preparation of this reagent, 
see § 22, 2.) After long standing (eight to ten days) it shows 
these reactions in a greater degree, and finally gradually loses 
this power again wholly. If the urine is in that condition in 
which it blues the acidified iodide of potassium and starch 
paste most powerfully, it also gives the above-mentioned reac- 
tion with pyrogallic acid, etc. 

It is easy to determine that fresh urine contains nitrates, 
according to Schonbein, if it is treated with potassium hydrate, 
and evaporated. Sulphuric acid sets free from the residue 
fumes which deeply blue the iodide of potassium and starch 
paste, and bleach indigo paper. The sulphuric acid here in 
the presence of alkaline chlorides sets free from the nitrates 
chlorine and hyponitric acid, which give rise to the reactions 
cited. 

§ 22. Hydkogen Peeoxide. 

This curious body was also first detected in the urine by 
Schonbein. The following reactions serve for its recognition : 
1. Hydrogen peroxide bleaches a dilute tincture of indigo 



90 ANALYSIS OF THE XTBINE. 

only very slowly, but if only a few drops of a dilute solution 
of ferrous sulphate are added, the mixture becomes completely 
freed from its color in a short time. 

2. If water is colored blue with tincture of indigo, so as to 
be non-transparent, treated with a little hydrochloric acid and 
then a few drops of a solution of potassic pentasulphide (Mehr- 
fachschwefelkalium) added with stirring, the mixture becomes 
completely free from its blue color. If in the preparation of 
this reagent no more sulphuret of potassium was added than 
was just enough to decolorize the indigo tincture, the colorless 
and clear filtrate will be distinctly and immediately blued by 
water, which contains only traces of hydrogen peroxide, when a 
few drops of a dilute solution of ferrous sulphate are added to 
the mixture. By an excess of hydrogen peroxide, however, the 
blue color is made to disappear again. (Reaction 1.) 

3. Hydrogen peroxide in the presence of ferrous sulphate 
immediately blues iodide of potassium and starch jDaste. This 
extraordinarily delicate reaction cannot be used, however, in 
urine, since every urine is able to form compounds with con- 
siderable quantities of free iodine, and consequently the blue 
color cannot occur. 

Detection in Urine. To about 200 cc. of freshly passed urine 
a solution of indigo is added, drop by drop, until the mixture 
shows a distinct green color, it is then divided into two equal 
parts. If fifteen or twenty drops of a dilute solution of ferrous 
sulphate are added to one half, the color will soon appear to be 
of a lighter green or brownish yellow, a change of color which 
evidently comes from a ]Dartial or total destruction of the indigo 
tincture, while, on the contrary, the half free from iron con- 
tinues to show its original green color. If, further, eight or ten 
drops of indigo tincture decolorized exactly by sulphuretted 
hydrogen (reagent 2) are allowed to drop into thirty or forty cc. 
of fresh urine, the mixture will not become colored blue at first, 
but only after adding a few drops of solution of ferrous sulphate. 
Sulphurous acid, which quickly reduces hydrogen peroxide, 
added to the urine in correspondingly small amount, hinders 
both reactions. 



ABNORMAL CONSTITUENTS OF URINE. 91 

III. ABNORMAL CONSTITUENTS OF URINE. 

§ 23. Albumen. 

[Serum Albumen.) 

Sclierer. Mulder. 

Carbon 54-883 53 -5 

Hydrogen 7-035 7*0 

Nitrogen 15-675 15-5 

Oxygen \ 22*0 

Sulphur 122-365 1-6 

^ Phosphorus ) 0-4 



Tormula unknown. 



99-958 100-0 

A. Presence. It is well known that albumen is the most im- 
portant substance which the animal body requires for its preser- 
vation ; it furnishes the material for its nourishment, as well as 
for the renewal of wornout organs. Its diffusion, therefore, in 
the whole body is large ; it forms the chief constituent of the 
blood, the lymph, the chyle, all the serous fluids, and the 
liquids of the cellular tissue. In the normal condition albu- 
men does not occur in the urine, but it occurs so frequently 
under pathological conditions, that it is necessary to test for it 
in every specimen whose composition we wish to ascertain. It 
occurs most frequently in all affections of the kidneys which 
are embraced under the name of Bright' s disease. 

W. Leube"^ found albumen in the sweat at different times. 
Waldenstrom t repeatedly observed urine containing albumen, 
both after the external and internal use of carbolic acid. 

B. Preparation of Pure Albumen. Blood serum is treated 
with very dilute acetic acid, drop by drop, till a flocculent pre- 
cipitate just forms, it is filtered, the filtrate evaporated in a 
vacuum, or on a water bath, at 40° C, to a small volume, nearly 
saturated with carbonate of sodium, and the residue subjected 
to dialysis. If, after frequent renewal of the external water, no 
more salts pass through the dialyser, the contents of the cell is 
evaporated in a vacuum again, or on a water bath at 40°, to dry- 

* Vircliow's ArcMv, Band 48, p. 181. 

f Neues Jahrbuch d. Pharm., Band 34, p. 111. 



92 ANALYSIS OF THE URINE. 

ness. Albumen, tlins prepared, is not yet wholly free from 
salts. (Hoppe-Seyler.) 

C Chemical Properties. Purified serum albumen is, in tlie dry 
state, a yellow, vitreous, translucent mass, wliicli dissolves in 
water to form a viscid fluid. 

1. A solution of serum albumen, witli which the albumen oc- 
curring in urine is identical, has, in neutral aqueous solu- 
tion, a specific rotation of the plane of polarization of —56° for 
the line D of the solar spectrum. 

2. Alcohol causes a j)recipitate in solutions of albumen, which, 
partly at least, dissolves in water again, if the alcohol is re- 
moved immediately. By the prolonged action of alcohol all of 
the serum albumen apj)ears to be coagulated. 

3. If a solution of albumen is treated with acetic acid until 
it has a strong acid reaction, and then a few drops of ferro- 
cyanide of potassium solution are added, a white, flocculent 
precipitate is produced. (Quantitative volumetric estimation 
by the method of Bodeker.) 

4. If albumen is heated with concentrated hydrochloric acid, 
or better, after the addition of a little sulphuric acid, a violet 
fluid results. 

5. Concentrated nitric acid colors a fluid containing albumen 
yellow, after the application of heat (xanthoproteic acid). After 
the addition of sodic hydrate, the yellow color of the solution 
becomes oranore red. 

o 

6. If a solution of albumen is warmed in a test tube over a 
spirit lamp, it commences to become turbid soon after the tem- 
perature has reached 60° or 65° ; it is observed that the cloudi- 
ness commences to be visible first at the surface of the fluid, 
and gradually spreads through the whole. Soon a flocculent, 
white, or, under certain circumstances, more or less colored 
coagulum occurs, since albumen at 72° or 73° C changes to the 
insoluble form. There are, however, several things to be ob- 
served in this simple reaction : if the albumen is very dilute, 
the cloudiness often occurs only after boiling the fluid, from 
which, at times, distinct flakes separate, especially after pro- 
longed boiling or standing. If the reaction of the fluid is 
feebly acid, a complete coagulation results in most cases, if 
the acid is not in excess ; if the solution has a neutral or alka- 
line reaction, only a slight cloudiness follows on heating, even 



ABNORMAL CONSTITUENTS OF URINE. 93 

when tlie amount of albumen is considerable ; it remains in 
solution combined with potassium. If, however, before heat- 
ing, as much acetic acid is added as is necessary to saturate the 
alkali, the separation takes place completely in the form of 
coarse flakes. An excess of acid, however, is to be carefully 
avoided, since otherwise the albumen remains more or less dis- 
solved by the acetic acid, even on boiling. 

Chloride of sodium and other neutral salts of the alkalies 
lower the temperature at which a solution of albumen coagu- 
lates, therefore this takes place in acid urine usually below 
70° C. 

7. If a solution of albumen is treated with acetic acid until it 
has a strong acid reaction, and an equal volume of a saturated 
solution of sulphate of sodium is added to the fluid, and then 
heated to boiling, complete coagulation results. 

8. A solution of mercury prepared by dissolving the metal, 
first in the cold and then with moderate heat, in its own weight 
of strong nitric acid, of specific gravity 1'41 (boiling point 115° 
to 120° C), diluting with two volumes of water, and after stand- 
ing a while decanting from the crystalline precipitate, forms the 
most delicate reagent for albumen, as well as for all protein 
bodies, whether dissolved or undissolved. If we heat a fluid 
containing albumen with this mercury solution to from 60° 
to 100° C, an intense red color is obtained, which disappears 
neither in the air nor on prolonged boiling. 

Millon's reagent can, according to Yintschgau and Gintl,^' 
be prepared as follows : a little nitrite of potassium is added 
to a solution of mercuric nitrate and the necessary amount of 
nitric acid added only when the reaction is performed. 

9. Dilute nitric acid added in not too small amount gives in 
solutions of albumen a white precipitate of nitrate of albumen 
which is soluble in an excess of nitric acid and an excess of 
water. 

(Important reaction.) Other mineral acids behave in the 
same manner. 

10. Most metallic salts, as alum, cause precipitates of varying 
composition. The precipitate produced by mercuric chloride 
(corrosive sublimate) is especially important. 

*Cliem. Centralbl., 1869, p. 860. 



94 ANALYSTS OF THE URINE. 

11. Sugar and concentrated sulplinric acid produce a beauti- 
ful red color with all protein bodies, just as with the biliary 
acids. (See Biliary Acids.) (Schultze.) 

12. Albuminoid bodies treated with a solution of sulphate of 
copper and then warmed after the addition of hydrate of potas- 
sium or sodium, give the solution a beautiful violet color. 
This reaction does not appear or only incompletely when the 
alkali is added before the copper salt. 

13. Solid albumen on being treated with sulphuric acid con- 
taining naolybdic acid becomes colored a beautiful dark blue. 
(Frohde.)" 

Albumen reacts to most of the above tests in common with 
the other protein substances. 

14. All albuminates, the peptones and unformed ferments not 
excepted, when dissolved in excess of glacial acetic acid, give 
after the addition of concentrated sulphuric acid beautiful 
violet -colored solutions, which have a feeble fluorescence. 
"When properly concentrated these fluids produce in the spec- 
trum an absorption band which, like that of urobilin and chole- 
telin, lies between the lines b and F. (A. Adamkiewicz.) 

D. Preparcdion of Albumen Ahsolutehj Free from Salts by Di fu- 
sion. B. Aronstein t obtained by the dialysis of an alkaline or 
neutral solution of albumen, by making use of the finest Eng- 
lish parchment paper, and continuing the process three or 
four days at a temperature of +10^ to 12^ C, during which the 
external water was changed two to three times, an albumen 
which on being ignited left no trace of ash behind. 

The chief projDerties of this pure preparation are as follows : 

1. Albumen is a body completely soluble in water, and neither 
the soluble nor the insoluble salts in the animal fluids aid in 
retaining it in solution. 

2. Pure albumen is coagulated neither by a boiling tempera- 
ture nor by alcohol ; the coagulation which is thus produced is 
caused only by the salts in its natural solutions. 

3. There is no compound of albumen with the insoluble salts 
of the animal fluids, to which these salts owe their solubility 
in the latter ; they are kejDt in solution rather by means of an 



* Zeitsclirift f . analyt. Chem., Band 7, p. 266. 
f Arcliiv fiir Physiologie, Band 8, p. 75. 



ABNORMAL CONSTITUENTS OF URINE. 95 

organic substance contained in blood serum, as well as in the 
albumen of eggs, and which does not belong to the class of 
albuminoid bodies. 

4. Blood serum, like egg albumen, contains, besides the albu- 
men, another albuminoid body, paragiobulin, dissolved by the 
crystalloid constituents. 

E. Detection. The recognition of albumen in urine depends 
on very simple tests, which, carried out with care, allow of an 
accurate conclusion. In the first place the reaction of the clear 
or previously filtered urine is determined, a small test tube is 
then about half filled and heated over the spirit lamp. If the 
urine has an acid reaction and albumen is present, as soon as 
the temperature has reached 50° or 60° C. a cloudiness will 
make its appearance at the surface of the fluid, which is soon fol- 
lowed by a coagulation of the albumen. If, however, the urine 
is neutral or alkaline, for the reason given above, the precipi- 
tation does not take place, but for the most part only a milky 
turbidity. But if in this case the boiled urine is treated with 
nitric acid until it has a strong acid reaction, a permanent pre- 
cipitate takes place, when albumen is present. But it is to be 
remarked that the nitric acid must be added in considerable 
excess, since albuminoid bodies may remain in solution when 
too little is added. 

Mtric acid has many advantages here over acetic acid, which 
has been heretofore used for rendering urine acid, since, in 
the first place, the addition of acetic acid must be made with 
great care, for an excess completely stops the separation of 
albumen, and, in the second place, acetic acid, according to the 
investigations of Eeissner, causes, in a urine which contains dis- 
solved mucus (mucin), a similar turbidity insoluble in an excess 
of acetic acid, which may readily be mistaken for a separation 
of albumen. 

For further confirmation of the presence of albumen the re- 
actions 3 and 7 are of especial service. 

Cases may occur, however, where a precipitate forms on boil- 
ing the urine, especially when it is only feebly acid or neutral, 
even when no trace of albumen is present. This precipitate 
consists of the earthy phosphates which are held in solution in 
feebly acid urines mostly only by free carbonic acid, after the 
expulsion of which by heat they are precipitated in flocculi, and 



96 AI^ALYSIS OF THE UHINE. 

in this form can scarcely be distinguislied from coagulated albu- 
men by the naked eye. The doubt is readily removed if, after 
cooling, nitric acid is added to the fluid in which the precipitate 
is suspended, and the mixture shaken ; if the precipitate con- 
sists of phosphates they will dissolve and the fluid become clear ; 
if, however, it is albumen, it will not disappear. This frequently 
happens, so that the subsequent test with nitric acid, especially 
when the cloudiness which occurred on heating was but small, 
must never be omitted. 

If, moreover, the urine contains resinous matters, as, accord- 
ing to Maly's investigations, may be the case after the internal 
use of turpentine, balsam copaiba, etc., a whitish-yellow cloudi- 
ness, not unlike precipitated albumen, occurs after the addi- 
tion of hydrochloric or nitric acid, which immediately disap- 
pears, however, after the addition of alcohol, and thus may be 
easily distinguished from albumen. 

The test with nitric acid can also be performed in the follow- 
ing very neat manner, according to Heller. A test tube is filled 
about half an inch high with jDure concentrated nitric acid, 
and a layer of the clear urine to be tested is poured carefully 
down the side of the tube by means of a pipette, so as to cover 
the acid. If the manipulation is well performed the urine floats 
on the nitric acid, and the mixture of the two takes place gradu- 
ally. At the point of contact there is formed almost always an 
intense red, violet or blue ring, the indican reaction. Care 
must be taken not to confound this play of colors with the re- 
action of the biliary coloring matters, unless a green color can 
be distinctly recognized under the blue. If the urine contains 
albumen, a cloudy zone, sharply bordered above and below, 
forms on applying this test at the point of contact of the two 
fluids, which zone can be recognized with great distinctness 
even when only traces of albumen are present. The reaction 
lasts quite a while, but after a long time the coagulated albumen 
gradually sinks to the bottom. A turbidity, similar at first sight, 
may also occur when the urine contains an abundance of urates ; 
a cloudy zone also forms in this case, but it stands at a higher 
level than the albumen zone. The lower edge, also sharply 
defined, stands above the point of contact of the two fluids, 
usually higher even than the upper border of the albumen zone ; 
it is, moreover, not sharply bordered above, but diffused and 



ABNORMAL CONSTITUENTS OF UHINE. q^^ 

rising toward tlie surface of tlie urine. If the urine contains 
albumen, and at tlie same time a large amount of urates, two 
zones may form, a lower one of albumen, wliicli is separated 
from tlie upper one of urates by a clear layer. It is better, 
however, in such a case to dilute the urine Avith two or three 
parts of water before testing it, in order to prevent the urate 
reaction, or at least to reduce it to a minimum. Turbidity from 
urates, moreover, disappears on the application of gentle heat, 
and all doubt can thus be removed readily. A precipitate of 
nitrate of urea may also take place in very concentrated urines, 
but this is crystalline and disappears immediately on the addi- 
tion of water. 

Mehu " uses for testing for albumen, qualitatively, a mixture 
of equal parts of crystallized carbolic acid and commercial acetic 
acid, with two parts of 90 per cent, alcohol. Two or three per 
cent, of nitric acid and about ten per cent, of this carbolic acid 
solution are added to the urine, the mixture is shaken, and al- 
lowed to settle. The deposit takes place more quickly if, instead 
of nitric acid, one-half of its volume of a saturated solution of 
sulphate of sodium is used. This is a delicate reaction and 
very minute traces of albumen may be detected with certainty. 

SUPPLEMENT. 

§ 24 FiBEiNE, Casein, Albuminose, Pakalbumen, Paeaglobulin, 
Peptone, Nephrozyiviose. 

1. Fihrine. Of the above protein substances, fibrine sometimes 
occurs in the urine. It separates in somewhat large masses, 
especially in cases of severe inflammation of the kidneys and 
urinary passages. Such a urine always contains blood also, 
and, as a result of this, albumen. Ackermann found fibrine in 
the urine in galacturia. I shall speak under the head of sedi- 
ments of the peculiar tube -like urinary casts, which Ererichs 
regards as flattened coagula of fibrine. 

Isolated cases have been observed, also, in which fibrine 
separated from the urine partly as a gelatinous mass, and partly 
as granular or fibrillated clumps. 

* Zeitsclirift f. analyt. Cliem., Band 8, p. 532. 

7 



98 AJ^ALYSIS OF THE URINE, 

2. Casehu Casein lias not yet been detected witli certainty in 
tlie urine. 

There are, moreover, at times protein substances, wliicli ap- 
pear in urine, which do not correspond in their characteristics 
to the ordinary ones. Thus Bence Jones describes a case ^ in 
which he found in the urine of a man suffering from "softening 
of the bones," together with casts a peculiar albuminous sub- 
stance which was characterized by being soluble in boiling water, 
precipitated by nitric acid, and dissolved on heating, but again 
separated on cooling. By its behavior with the reagents spoken 
of above under albumen, as acetic acid, ferrocyanide of potas- 
sium, etc., it was proved to be, without doubt, a protein sub- 
stance ; but we cannot regard it as albumen or casein on account 
of its anomalous behavior with water and nitric acid, at least 
not until we have succeeded in converting albumen or casein 
artificially into these peculiar modifications. 

3. Alhinninose. Baylon describes an albuminoid substance un- 
der the name of albuminose, which is said to occur also in nor- 
mal urine. According to Mialhe this substance has the same 
relation to albumen that glucose has to starch (?). Albuminose 
is not precipited by heat, acids, or alkalies, it is precipitated by 
tannin and many metallic salts. It is said, as already remarked, 
to occur in every normal urine as well as in pathological cases. 
In a urine of Bright's disease, however, where there was much 
albumen, no albuminose could be found. Baylon designated 
cupric tartrate as a very delicate reagent for albuminose. After 
the addition of a few drops of potassic hydrate the urine is 
boiled, filtered, and then a solution of cupric tartrate added, 
until the mixture has a faint blue color. After one or two 
hours tartrate of albuminose (?) precipitates, which dissolves 
on heating, but separates again on cooling.f 

C. Gerhardt % states that different varieties of albumen occur 
in the urine of patients suffering from kidney disease. In sev- 
eral cases the urine was precij)itated neither by boiling nor by 
the addition of nitric acid, but alcohol separated substances 
which gave decided reactions for albumen. 



* Annal. d. Chem. u. Pliarm., Band 67, p. 97 to 105, 

f Canstatt's Jaliresbericlit, 1860, p. 270. 

j Centralblatt f. d. med. Wissenscliaft.,1869, p. 174. 



ABN0R3IAL CONSTITUENTS OF URINE. 99 

4. ParaTbumen and Paraglobulin. E. Masing ^ also describes a 
case of Briglit's disease in wliicli tlie urine, together with serum 
albumen, contained mucli paralbumen. Tliis urine gave im- 
mediately, after the addition of water, a milky cloudiness, which 
disappeared on being treated Avitli acids, alkalies, and also with 
a solution of common salt. 

Edelfsent made the same observation in thirty-one cases of 
albuminuria. The cloudiness of the urine, on dilution with 
water, first occurred after a few minutes, and was for the most 
part increased by the introduction of carbonic acid. Edelfsen 
considers this albuminoid body, as well as the paralbumen 
found by Masing, to be paraglobulin, although he did not suc- 
ceed in causing the coagulation of fluid containing fibrinoge- 
nous substance by means of it when precipitated. 

Detection of ParaghhuUn in Alhuminous Urine, The urine, 
after filtration, is diluted with Avater till its specific gravity 
sinks to 1,003 or 1,002, so that its amount of solid constituents 
is excessively small. Under certain circumstances, the dilution 
alone may give rise to the separation of paraglobulin, at least 
Edelfsen observed:]: a cloudiness frequently as soon as he had 
diluted the albuminous urine with water, in the proportion of 
1 : 20. If now carbonic acid is conducted through the dilute 
fluid, for from two to four hours, almost all albuminous urines 
give turbidities of paraglobulin, which often, after from twenty- 
four to forty-eight hours, settle as distinct precipitates. (H. 
Senator.) § 

The preci23itate thus obtained is milk white, of a fine, floccu- 
lent character, and dissolves completely on the addition of a 
one per cent, hydrochloric acid solution, also of a few drops of 
a solution of common salt, and likewise in concentrated acetic 
acid. It separates so completely from the solution of salt, on 
heating, that no trace of an albuminous body is any longer de- 
monstrable in the filtrate. The flakes separated on heating 
do not dissolve again in acetic acid, at least if added in mode- 
rate amount. If the precipitate is dissolved in a trace of sodic 
hydrate, filtered, and treated with clear pericardial or perito- 

^'' Beitrage zu Albuminometrie, Dorpat, 1867, bei H. Laakmann. 
f Centralblatt f. b. med. Wissenschaft, 1870, p. 367. 
X Deutscb. Arcbiv. f. klin. Med., Band 7, p. 69. 
§ Vircbow's Arcbiv, Band CO, p. 476. 



100 ANALYSIS OF THE URINE. 

neal fluid, a turbidity occurs on sliaking, which, after prolonged 
standing, is followed by a copious flocculent precipitate. 

According to Senator, paraglobulin can be detected in every 
urine which contains coagulable albumen. Of the chronic kid- 
ney diseases, amyloid degeneration appears to yield the urine 
which is relatively richest in paraglobulin. Alkali albumi- 
nate, or a body which is obtained from the blood serum after 
precipitation of the paraglobulin by acetic acid, does not ap- 
pear to occur in the urine at all, or only in slight traces. 

5. Fejjtone. Peptone-like bodies were found by O. Schultzen 
and L. Riess ^' in the urine, after phosphorus poisoning. These, 
by precipitating from the strongly concentrated urine by alco- 
hol, redissolving in water, and reprecipitating with alcohol, were 
obtained free from all coloring matters. The identity of this 
peptone-like substance with the true albumen peptones is still 
doubtful. 

Detection of Peptonic in Albuminous Urines. The albumen is 
removed from albuminous urines by heat, wdth or without the 
addition of acetic acid, by the familiar method, and the fil- 
trate mixed Avith three times its volume of alcohol by shaking. 
The precipitate which takes place, dissolved in water after 
washing with alcohol, is colored yellow on heating Avith nitric 
acid, and, in short, shows all the reactions of an albuminous 
body. 

Gerhardt t observed peptone frequently in urine which was 
free from albumen ; lie found it sometimes as a forerunner, and 
sometimes as a follower of ordinary albuminuria. 

Senator J was able to detect peptone in every albuminous 
urine in small amount. 

6. NejjJirozymose, Finally, according to Bechamp, a pro- 
tein substance can be precipitated from every normal urine by 
three times its amount of 88 to 90 per cent, alcohol, which, 
after washing, is soluble in water ; it is capable of changing 
starch into sugar at 60° to 70° C, and Bechamp has given it 
the name of nephrozymose. 

* Annalcn des CliaritS Krankenliauses zu Berlin, Band 15, p. 9, etc. 
f Wiener med. Presse, 1871, p. 1. 
:j:Loc. cit., p. 488. 



ABNORMAL CONSTITUENTS OF URINE. IQl 



§ 25. Ueinaey Sugak. Grape Sugar. 

Anhydrous : Carbon 40-00 Crystallized: 36-36 

Hydrogen Q'QQ 7-07 

Oxygen 53-34 56-57 



100-00 100-00 

Formnla: CeH,A [C,,H,,0,,] C,H„0,+H,a [C,,H,,0,,+2aq.]. 

A. Presence. Grape sugar, which, is perfectly identical with 
urinary sugar, is found, as is well known, very wide-spread in 
the vegetable kingdom. But it also occurs in the animal king- 
dom, partly normally, partly in disease in various fluids. 

Grape sugar always exists in the contents of the small intes- 
tine, and in the chyle, after taking food containing sugar or 
starch ; it is found in the hen's egg — both in those in the pro- 
cess of hatching and in those not being hatched, in the yolk as 
well as in the white — in the amniotic and allantois fluids of 
cows, sheep, and swine, and in the liver. Bernard also finds 
it constantly in the blood, especially in the hepatic vein ; the 
blood of the portal vein, on the contrary, contains no sugar, so 
that its formation must occur in the parenchyma of the liver. 

According to the most recent and comprehensive investiga- 
tions of Seegen,"^ there appears to be no doubt whatever that 
the excretion of sugar by the urine is not a physiological func- 
tion, and that normal urine, contrary to the assertions of Briicke 
and Bence Jones, contains no sugar. Sugar occurs in large 
amount only in diabetes mellitus, but it is then increased in the 
blood, the vomitus, the saliva, the sweat, etc. Sugar has also 
been found in the urine, at times, in other diseases ; it appears 
to occur especially in disturbances of the abdominal circulation. 
By wounding certain points of the medulla oblongata in ani- 
mals sugar may be made to appear temporarily in the urine. 
According to Lehmann sugar appears in the urine of women 
from twenty-four to forty-eight hours after weaning an infant. 
These observations of Lehmann correspond to the assertions of 
De Sinety,t according to whom, whenever there is an obstruc- 

* Seegen, Der Diabetes Mellitus, 2 Aufl., p. 196. 
\ Gazette med. de Paris, 1873, p. 573. 



102 ANALYSIS OF THE URINE. 

tion to the flow from the lacteal gland, sugar appears in the 
urine. If, on the contrary, the production and discharge of milk 
retains its equilibrium, sugar disappears from the urine, and 
the latter becomes normal. Wollert and Almen ^ observed the 
occurrence of sugar in the urine after the internal use of oil of 
turpentine. 

According to the investigations of A. Ewald,t subcutaneous 
injections of nitrobenzol and nitrotuluol give rise to saccharine 
urine in rabbits. In dogs, however, it was seen only when 
nitrobenzol was given in large doses internally (0'8 to 3 grams). 
F. A. Hoffmann % also observed a large amount of sugar in the 
urine in rabbits after the injection of 0*2 to 0*6 gram of nitrite 
of amyL 

B. Microscopic Properties. Diabetic sugar crystallizes in 
irregular masses, which appear as warty conglomerations, and 
consist of cauliflower-like groups of laminae. These laminae 
have a rhombic shape. If the crystallization takes place rapidly 
it does not appear in laminae even when seen under the micro- 
scope, but in irregular, striated roundish masses. 

C. Preparation of Chemically Pure Grape Sugar. — 1. If pure 
cane sugar is dissolved in 80 per cent, alcohol, to which a little 
hydrochloric acid has been added, with frequent shaking until 
it is saturated, after long standing chemically pure grape sugar 
sej)arates in white crystalline crusts. (H. Schwarz.) After a 
long time, when no further sejoaration follows, the crystals are 
collected, thoroughly washed with alcohol, dried in a dessicator, 
and finally re crystallized from boiling absolute alcohol. 

2. The best starch sugar is dissolved on the water bath in 
about half its weight of w^ater, and then filtered into a glass fun- 
nel whose orifice is closed with a stopper. When the funnel is 
nearly filled it is covered with a glass plate and put on a stand 
in a cool place for several months, when the grape sugar crys- 
tallizes out as hydrate. 

The mother liquor is allowed to flow away, the sugar is 
covered with a layer of 80 per cent, alcohol, and treated with it 
until the sugar is dazzlingly Avhite. Then it is dried, first in 
the open air, and finally in a dessicator over chloride of calcium. 

* Neues Jalirb. d. Pliarm., Band 34, p. 163. 

f Central blatt f. d. med. Wissenschaft.,1873, No. 52. 

I Arcliiv f iir Anatom. u. Pliysiologie. 1872, p. 746. 



ABNORMAL CONSTITUENTS OF URINE. 103 

Heat is to be applied only when most of tlie moistnre is re- 
moved, because otherwise the sugar is softened by the moisture 
and cakes together. (Mohr.) 

D. Chemical Properties. Pure grape sugar is white, odorless, 
by no means as sweet as cane sugar, and is also less soluble in 
water. Its solution has no reaction on vegetable colors, and 
turns polarized light to the right. It is quite soluble in alcohol, 
not at all so in ether. If crystallized grape sugar is exposed 
for a long time to a temperature of 100^ C, it loses its water of 
crystallization. 

2. The specific rotation of an aqueous solution of grape sugar, 
if the solution has been heated or has stood a long time, is 
+ 56'4 for yellow light. A freshly prepared cold solution causes 
a greater rotation to the right of the plane of polarization when 
tested immediately after dissolving it, but on long standing, 
and more quickly if heated, it sinks to + SG^."^ 

3. In contact with bodies containing nitrogen, especially 
casein, it undergoes lactic acid and, later, butyric acid fermen- 
tation. In diabetic urine it changes into an acid even at medium 
temperatures, more quickly at a temperature of from 25° to 40'' 
C, which, according to circumstances, may be acetic, butyric, 
or even lactic acid. 

4. Grape sugar forms with several bases peculiar compounds 
called saccharates. 

a. Saccharate of Potassium, KgO+OgHiaOg [2KO + CioH]20io], is. 
readily obtained if an alcoholic solution of sugar is mixed with 
a solution of caustic potash in alcohol. The compound precipi- 
tates immediately in white flakes, which stick together when 
exposed to the air, deliquesce, and attract carbonic acid. 

b. Saccharate of Calcium. If a solution of sugar is treated with 
an excess of quicklime, the solution filtered and the filtrate 
treated with alcohol, this compound separates as a white mass. 

c. Compound of Grape Sugar with Chloride of Sodium, ^aCl, 
2(06H,2ae) + H,a [N'aCl,20i,IlH0i, + 2H0]. If a solution of grape 
sugar is mixed with a solution of chloride of sodium, and the 
mixture left to spontaneous evaporation in the air, the com- 
pound crystallizes in large, colorless, six-sided double pyramids 
or rhombohedra. The crystals are hard, readily pulverizable, 

^ Zeitsclirift f. analyt. Cliem., Band 14, Heft 3 u. 4. 



104 ANALYSIS OF THE URINE. 

easily soluble in water, and difficultly so in alcohol. They con- 
tain 13 '52 per cent, of chloride of sodium. 

5. If a solution of grape sugar is warmed with potassic or 
sodic hydrate, it becomes a beautiful brown-red color ; if nitric 
acid is then added, a piercing, sweetish odor is evolved, which 
reminds one partly of caramel and partly of formic acid. 

6. If a solution of indigo carmine, made alkaline with carbo- 
nate of sodium, is heated with a little grape sugar to boiling, it 
becomes colored, if only a small amount of sugar is added, first 
green then purple, and, with more sugar, red, and finally yel- 
low. If the hot yellow solution is shaken, so that the oxygen 
of the air can act upon it, the play of colors is reversed. The 
mixture becomes colored purple red, then green, and finally 
blue again ; yet on standing quietly the yellow color soon reap- 
pears. (Mulder.) This reaction is very brilliant, and allows very 
small amounts of sugar to be detected. With mere traces of 
sugar only a very weak blue indigo solution should be used. 

7. If a solution of sugar is treated with a little caustic potash 
and a few drops of a solution of sulphate of copper, either no 
precipitate occurs, or that which takes place dissolves again to 
a beautiful blue fluid. If this mixture is heated, the fluid is 
first colored orange yellow, soon becomes cloudy, and finally a 
beautiful red precipitate of cupreous oxide separates. This 
reduction takes place after long standing in the cold without 
the application of heat. According to the investigations of 
Salkowski this reaction has two phases. First a bluish-green 
precipitate occurs, a compound of hydrated cupric oxide with 
sugar, which dissolves in an excess of sodic hydrate Avhich soon 
decomposes it. An excess of sodic hydrate is absolutely neces- 
sary in the employment of the reaction. Uric acid, hypoxan- 
thin, mucus, etc., likewise cause a reduction of cupric oxide 
when heated, while red cupreous oxide is separated. It is 
well, moreover, to bear in mind that many substances by their 
presence may hinder the separation of cupreous oxide, as, 
for example, albuminous matters, especially peptone, l^reatin, 
kreatinin, pepsin, urinary coloring matter, etc. 

8. If a solution of sugar is placed in a small flask with a 
little yeast, fermentation will soon occur, especially at a tem- 
perature of 15° to 20° C Its progress can be very well ob- 
served in the following apparatus, fig. 2. 



ABNORMAL CONSTITUENTS OF UBINE. 



105 



Fig. 2. 




■ A is a small glass flask, in wliich the solution of sugar is 
brought in contact with the yeast ; 
this flask is connected with a small 
flask, B, which is half filled with lime 
or baryta water by means of the 
glass tube, c. The tube, a, is closed 
at the top by a piece of wax, h. If 
the mixture. A, is heated to the above 
temperature, the solution of sugar 
will become cloudy after a short 
time ; it commences to foam consid- 
erably, and bubbles of gas develop 
very regularly. This gas consists of 
carbonic anhydride, and, on going- 
through the baryta or lime water, 
will render it cloudy by the separation of carbonate of barium 
or calcium, which will be precipitated. When the evolution of 
gas finally ceases, the fluid in A becomes clear, has lost its 
sweet taste, and instead has assumed a vinous one. The sugar 
is decomposed into alcohol and carbonic anhydride, during 
which decomposition, however, a few alcohols homologous to 
ethylalcohol are always formed in small amount, as well as 
traces of glycerine and succinic acid. 

If the amount of sugar is small, a test tube is filled with 
mercury and inverted in a small mercury bath. By means of a 
pipette with a curved point, a little neutral or faintly acid solu- 
tion of sugar treated with active well-washed yeast is allowed 
to rise in the tube, and is left at rest at a temperature best of 
25° or 30° C. If, after one or two days, the development of gas 
is ended, a little concentrated potassic hydrate is allowed to 
rise up into the fluid by means of the pipette, and this will 
completely absorb the disengaged gas. 

9. If a solution of grape sugar is treated with a weak ammo- 
niacal solution of nitrate of silver, and is heated to boiling and 
kept for a time at this temperature, it deposits metallic silver 
in the form of a beautiful polished metallic mirror. This re- 
duction can be of service under certain circumstances, since it 
is not prevented by the presence of ammonia. It is not to be 
forgotten, however, that many other matters, as, for example, 
tartaric acid, etc., reduce nitrate of silver in a similar manner. 



106 ANALYSIS OF THE URINE. 

10. If a solution of sugar is treated with an equal volume of 
carbonate of sodium solution (three parts of water and one of 
crystallized salt), a little subnitrate of bismuth added, and 
boiled awhile, the oxide of bismuth is reduced with a black 
color. The slightest blackening, or a gray coloration of the 
snow-white bismuth salt, shows the presence of urinary sugar 
in the most decided manner, since, according to Bottger, no 
other constituent of urine has a reducing action on that salt of 
bismuth. The urine must, however, be absolutely free from 
albumen, since otherwise black sulphide of bismuth is readily 
formed, which may give rise to erroneous conclusions. 

The reaction is quite successful also wdth an alkaline solu- 
tion of bismuth oxide, which is obtained by precipitating a 
solution of bismuth with a large excess of sodic hydrate, and 
adding drop by drop, with gentle heat, a solution of tartaric 
acid, until the precipitate which takes place is just dissolved 
again. According to Almen, four grams of Rochelle salt are dis- 
solved in one hundred of potassic hydrate of specific gravity 
1'33, gently warmed, and subnitrate of bismuth added as long 
as it dissolves ; about two grams will be necessary. 

11. If a solution of sugar containing hydrate of potassium 
is treated with a few drops of molybdate or tungstate of am- 
monium, heated to boiling, and then acidulated carefully with 
hydrochloric acid, there results a blue color of molybdate of 
molybdenum, or tungstate of tungsten. In hydrochloric acid 
solutions sugar reduces at the boiling temperature only the 
molybdic acid, with the formation of a blue color; yet this 
reaction is not nearly as delicate as in an alkaline solution. 
(Huizinga.)^" 

E. Detection. The methods of detecting sugar in the urine 
are different, according to the amount supj^osed to be present. 
If the twenty-four hours' amount of urine is large (four to six 
liters), if the color is greenish yellow, and, at the same time, 
the specific gravity is high, at least above 1'020, it is probable 
that the urine to be tested is diabetic. In this case the detec- 
tion of the sugar is simple, since diabetic urine, decolorized 
by animal charcoal, behaves very nearly like a pure solution of 
sugar with almost all reagents. If the urine in question is also 

*Arcliiv d. Pliysiologie, Band 3, p. 496. 



ABNORMAL CONSTITUENTS OF URINE. 107 

free from albumen, wliicli must be ascertained according to 
§ 23, tlie different tests for grape sugar can be directly em- 
ployed; in other cases, however, it must be first freed from 
albumen, observing the precautions given in § 23. To prove 
the presence of sugar, we proceed as follows : 

1. Fifteen or twenty drops of the urine to be tested, decol- 
orized with animal charcoal, and diluted with 4 or 5 cc. of w^ater, 
are treated with half a cc. of sodic or potassic hydrate, and 
then a very dilute solution of sulphate of co23per is added drop 
by drop. If sugar is present, the precipitate first formed after 
shaking dissolves to a clear blue fluid. Too large an amount 
of the copper solution is to be avoided, especially if only small 
amounts of sugar are supposed to be present, since otherwise a 
black oxide of copper also separates on boiling, which conceals 
the red cupreous oxide which is formed at the same time. The 
clear blue solution is then heated nearly to boiling, without 
shaking, when a yellow cloud forms on the surface, and soon a 
precij)itate of yellow or red cupreous oxide will follow without 
being heated further. The mixture of urine and potassic hy- 
drate must not be heated before the addition of the solution of 
copper, since the sugar, especially if only a small amount is 
present, may be so changed that it no longer has a reducing 
action on the cupric oxide. 

A second mixture, prepared in the same way, is allowed to 
stand quietly, without previous heating, from six to twenty-four 
hours. If sugar is present, there will be a precipitate of cu- 
preous oxide in this case also. This control experiment is of 
great importance, and ought never to be omitted, since most 
of the substances which reduce the copper solution, like sugar, 
do so only when heated, or after prolonged boiling, and not 
like diabetic sugar in the cold. 

If the amount of sugar is small, it is advisable to filter the 
urine beforehand through animal charcoal (four or five times) 
to completely decolorize it. The filtrate, which is clear as 
water, gives much better reactions than the original urine. 
(Maly, Seegen.) 

Seegen ^' lias found, further, that pure animal charcoal retains 
considerable amounts of sugar. If, therefore, after complete 

"" Ajcliiv d. Pliysiologie, Band 5, p. 375. 



108 AJ^ALYSIS OF THE URINE. 

clecolorization, the cliarcoal on tlie filter is washed with a little 
distilled water/ it gives a yerj- pure reaction. If the urine has 
a high specific gravity and a deep color, the reaction of the 
first washing from the charcoal is usually not so sensitive ; but 
Seegen found that, in these cases, the second and third wash- 
ings gave a much more characteristic reaction. 

2. A second sjDecimen of urine filtered, decolorized, and freed 
from albumen, is diluted with an equal volume of a solution of 
carbonate of sodium, a small amount of subnitrate of bismuth 
is added, and the mixture is heated to boiling for a long time. 
According to the amount of sugar present, a partial or com- 
plete reduction of the oxide of bismuth will follow, and, there- 
fore, a gray or black color will occur. With small amounts of 
sugar, as little of the salt of bismuth as possible is to be taken, 
in order that a slight reduction shall not be concealed by a 
considerable excess of the white salt. If the specimen is then 
allowed to stand quietly, the undecomposed oxide of bismuth 
first settles, and then the reduced bismuth follows beautifully 
and distinctly in the form of a velvet-black ring. The reaction 
also succeeds very well with the alkaline solution of bismuth. 
(See Keaction 10.) 

3. Another portion of the decolorized urine is placed in a 
tolerably long but narrow test tube, a little potassic hydrate is 
added, and the upper part of the column of fluid is heated to 
boiling. If sugar is present, this part will be colored yellow 
or brownish red, while the lower part retains its original color. 
In this manner the slightest changes of color may be distinctly 
perceived. This reaction is to be highly recommended as a 
confirmatory test. 

The Reactions Nos. 6 and 9 give further confirmation, but 
especially the fermentation test, which may be undertaken in 
diabetic urine with the apparatus pictured in fig. 2. 

Sugar may readily be obtained from diabetic urine, pure 
and in crystalline form. The following methods serve for this 
purpose : 

I. A portion of urine is evaporated on the water bath to a 
syrupy consistence ; the residue is allowed to stand, and, after 
a long time, the sugar will crystallize out in yellow warty 
masses. It is freed from urea and extractive matters by treat- 
ing with absolute alcohol ; the sugar is then extracted from the 



ABNORMAL CONSTITUENTS OF URINE. 109 

residue by boiling spirit, and tbe solution allowed to evapo- 
rate. The sugar will remain behind tolerably j)ure, and can be 
readily freed from the alcohol which adheres to it by repeated 
re crystallization from water. 

II. Lehnann's 3IetJiod. An alcoholic solution is first prepared, 
by evaporating the urine and extracting wdth alcohol. This is 
evaporated to dryness, the residue dissolved in w^ater, and the 
solution saturated with chloride of sodium. After evaporation, 
the chloride of sodium compound with sugar will crystallize, 
and may be obtained in pure crystals by repeated crystalliza- 
tion. They are dissolved in water, and precipitated carefully 
by sulphate of silver. The precipitate of chloride of silver is 
filtered off, and the filtrate evaporated to dryness; by extrac- 
tion with alcohol the sugar is obtained chemically pure. 

Without regard to the fact that these methods only succeed 
when the urine contains somewhat considerable quantities of 
sugar, yet cases occur in which the sugar is completely uncrys- 
tallizable, and differs from grape sugar by its power of turning 
polarized light to the left. In such cases, the residue of urine 
always remains syrupy and shows no trace of crystallization. 

III. If the urine does not have the above characteristics, but 
still reduces the copper solution on being heated, without, how- 
ever, separating cupreous oxide, but at most producing a yel- 
low coloration of the mixture, it is necessary, in order to be 
able to prove the presence of sugar with certainty, to separate 
it in the purest possible form before the above reactions can 
be undertaken with a positive result. For example, a slight 
reduction of the copper solution can be caused by uric acid, 
etc., even when sugar is entirely absent. Even if a reduction 
should in fact be caused by sugar present, cupreous oxide may 
be held in solution by kreatinin, etc., wherefore this reaction 
loses all certainty. In this case there occurs at most a yellow 
coloration of the mixture without the characteristic precipita- 
tion of cupreous oxide. Such a solution on standing exposed 
to the air becomes colored blue again on the surface by oxida- 
tion. To avoid all of these uncertainties, any albumen present 
is first removed from a large amount of urine (500 to 800 cc.) 
according to § 23, the filtrate, or if no albumen is present, the 
original urine previously filtered, is evaporated on the w^ater 
bath to a thick syrup, and allowed to stand in the cold from 



110 A^^ALTSIS OF TEE URINE. 

four to six lioiirs. Tlien after tlie residue lias been diyided as 
miTcli as possible with 230wdered pnmice-stone, it is extracted 
witli ninetj per cent, alcoliol, with which, in not too small 
amount, the extract is allowed to remain in contact for at least 
some hours with frequent shaking. The clear filtered liquid is 
then treated with an alcoholic solution of pure potassic hy- 
drate, until precipitation ceases, without, however, making use 
of too great an excess. If sugar is present, saccharate of po- 
tassium precipitates as a pitchy, sticky mass, always together 
with other compounds of potassium in a crystalline or floccu- 
lent form. When the potassium saccharate has settled, the spirit 
is quickly poured off from the precipitate, the latter is washed 
repeatedly with absolute alcohol, whether it is flocculent, crys- 
talline, or pitchy, it is then dissolved in water, and the potassi- 
um quickly saturated with carbonic acid, in order to prevent a 
decomposition of the sugar. In most cases this solution gives 
the reactions already given, but since, under certain circum- 
stances, substances are precipitated with the potassium com- 
pound which have a reducing action on cupric oxide, the 
presence of sugar is not yet placed beyond all doubt. Accord- 
ing to Lehmann, therefore, the aqueous solution of the potas- 
sium precipitate, accurately neutralized with acetic acid, is pre- 
cipitated with acetate of lead solution in moderate excess, 
filtered, the excess of oxide of lead removed by sulphuretted 
hydrogen, again filtered, and the fluid, usually clear as water, 
is evaporated on the water bath almost to dryness, so that at 
all events all of the sulphuretted hydrogen is removed. The 
residue is dissolved in water, and the tests given in I. are per- 
formed. If they are successful, the presence of sugar may be 
considered as proved, since it is difficult for any other sub- 
stance to be contained in this fluid last obtained, which, like 
sugar, gives the reactions mentioned. In the copper test, if the 
mixture is allowed to stand in the cold, cupreous oxide will 
separate if sugar is present without the application of heat ; 
moreover, only small amounts of the cupric oxide solution are 
to be taken, so that the mixture shows only a slight blue color. 
Finally the fermentation test yields the final decisive proof ; 
this test can be carried out with great accuracy, even with very 
small amounts of sugar, in the apparatus described under 
Chemical Properties, No. 8. Fermentation occurs quickly in 



ABNORMAL CONSTITUENTS OF URINE. HI 

tile presence of sugar, and to prove that the gas is not de- 
rived from the decomposition of the yeast, it is expedient to 
perform a control experiment with yeast and j^ure water. 

The alcohol formed by the fermentation can also be readily 
detected. For this purpose a few cc. of the fermented fluid 
are distilled, the distillate is treated with a few drops of a solu- 
tion of iodine in iodide of potassium, potassic hydrate is added, 
drop by drop, until it is just decolorized, and the mixture is 
allowed to stand for a time. If alcohol is present, there soon, 
or after standing awhile, occurs a yellowish cloudiness of iodo- 
form, which after complete settling is subjected to microscopic 
examination. Iodoform forms either regular six-sided tables 
very similar to cystin crystals or six-sided stars of great beauty. 
(Lieben.)^* 

It must be remarked, however, that normal urine also, as 
Lieben has found, contains a volatile substance, which passes 
over on distillation and yields iodoform with iodine and hydrate 
of potassium. If we wish to subject the urine directly to fer- 
mentation with yeast, and to use the distillate for the iodo- 
form reaction, the urine must first be evaporated to one-half its 
volume before adding the yeast, so as to remove this volatile 
substance. 

In many cases where the original urine showed only very 
doubtful reactions for sugar, I have succeeded by this method 
in proving its presence with great distinctness by all of its re- 
actions. 

Leconte treated the potassium precipitate in the following 
manner : Tartaric acid in slight excess is added to its solution 
in as small an amount of water as possible, it is shaken, the 
tartrate of potassium is filtered off, and the cold filtrate treated 
with excess of carbonate of calcium till it has a perfectly 
neutral reaction. The filtrate is evaporated on the water bath, 
and the residue exhausted with absolute alcohol. This solution, 
after spontaneous evaporation, leaves behind, when sugar is 
present, a syrup, which after quite a long time, often only after 
months, deposits crystals which frequently fill the entire mass. 
If, however, one is content with the fermentation of the sugar 
instead of its extraction, according to Leconte the aqueous solu- 

* Annal. d. Chem. u. Pharm., Supplementbd. 7, p. 313. 



112 ANALYSIS OF THE URINE. 

tion of tlie potassium precipitate is treated witli dilute sul- 
phuric acid to saturation, the sulphate of potassium which 
separates after standing awhile is filtered off, a little water 
with yeast is added, and the mixture is put in the fermentation 
apparatus described. 

To find sugar in normal urine Briicke uses the following 
methods, which are best mentioned here : 

a. The urine (1,000 to 5,000 cc.) is first j)recipitated by a con- 
centrated solution of sugar of lead, filtered, the filtrate treated 
with subacetate of lead till precipitation ceases, again filtered, 
and finally precipitated with ammonia. The last precipitate is 
collected on a filter, Avashed with water, and finally allowed to 
dry between thick layers of blotting j)aper which are renewed 
from time to time. The crumbled cake is first rubbed rather 
coarsely in a mortar with distilled water, and then a concen- 
trated solution of oxalic acid is added with constant trituration, 
as long as a specimen filtered off continues to be rendered 
cloudy by further addition of oxalic acid. The filtrate is satu- 
rated with finely divided carbonate of calcium, again filtered, 
rendered feebly acid with acetic acid, evaporated to dryness, 
and the residue dissolved in a little water. Briicke performed 
the usual reactions with this solution as well as the fermenta- 
tion test. Bence Jones does not decompose the lead precipi- 
tate by oxalic acid, as Briicke does, but in a simple way, after 
it has been suspended in water, by means of sulphuretted 
hydrogen. Bence Jones found in several normal urines (1,000 
to 5,000 cc.) by this method small amounts of sugar (2 to 3 
grains in 1,000 cc. of urine). 

b. The urine is treated with strong alcohol till the mixture 
contains about four-fifths of absolute alcohol. It is well to take 
200 cc. of urine, and mix it with 800 to 1,000 cc. of 94 per cent, 
alcohol. After it is mixed, a short time is allowed to elapse 
for the precipitate which has formed to settle, and then it is 
filtered into a beaker. An alcoholic solution of hydrate of 
potassium is then added, drop by drop, to the filtrate, with con- 
stant stirring, till a feeble though distinct alkaline reaction can 
be detected by litmus paper. The beaker is then allowed to 
stand twenty-four hours in a cool place, well covered up. The 
next day the fluid is carefully poured off, the beaker turned 
over on filter paper, so that the rest of the fluid may be ab- 



ABNORMAL C0N8TITVENTS OF URINE. 113 

sorbed, and then it is allowed to stand exposed to the air till 
the decided odor of alcohol can be no longer perceived. The 
bottom and, to a certain extent, the sides of the glass are covered 
with a crystalline coating, which is to be dissolved in as little 
water as possible, and this solution employed for the reactions 
given. But since under certain circumstances uric acid may 
exist in this crystalline deposit, it is well in any case to acidify 
the concentrated aqueous solution with hydrochloric acid, and 
leave it at rest for twenty-four hours, so that any uric acid 
present may separate. The neutral filtrate is then employed for 
the bismuth, copper, and potassium hydrate reactions, as well 
as for the fermentation test also when possible. The alcohol 
formed by fermentation is detected by the iodoform reaction, 
as given above, page 111, under III. 

Budecker first precipitates the potassium with tartaric acid 
from the concentrated aqueous solution of the crystalline de- 
posit, removes the excess of the acid from the filtrate by car- 
bonate of calcium, with which he allows the fluid to be in 
contact for a time, filters from the excess of tartrate and car- 
bonate of calcium added, and uses the solution thus obtained 
for the copper, bismuth, and potassium hydrate reactions. 

But Seegen,"^'* from his own investigations, considers that all 
the proofs of the occurrence of sugar in normal urine which 
Briicke and others advance are not sufficient, because the ap- 
pearances which they give as sugar reactions can be produced 
in the same intensity by other substances also, which are not 
excluded by the processes employed. 

The excretion of sugar by the urine is, according to Seegen, 
not a physiological function ; according to him, normal urine 
contains no sugar. 

The method recently given by Huizinga t for the detection 
of sugar in normal urine has not yielded me, on repeated trials, 
results which remove all doubt. 

* Seegen, Der Diabetes, 3 Aufl,, p. 224. 
f Arcliiv d. Physiolog., Band 3, p. 496. 



114 AITALYSIS OF THE URINE. 

APPENDIX. 

§ 26. Alkapton. 

Bodecker "^ found in the urine of a man forty-four years old, 
who suffered repeatedly from severe cough and expectoration 
after typhoid fever, a peculiar substance which had the pro- 
perty of absorbing large quantities of oxygen and becoming 
brown in the presence of an alkali. Bodecker calls this body 
alkapton. The patient at that time suffered great pain, which 
began from the sacrum, extended to the lower vertebrae, and 
thence radiated as lumbo-abdominal neuralgia. The amount 
of urine in twenty-four hours amounted to about 1,500 cc. 
(sp. gr.:=l*020 to 1*025), and contained not over one per cent, 
of sugar. On the addition of potassic hydrate the reddish-yel- 
low color of the urine became a dark brown from above down- 
ward, and a large amount of oxygen was absorbed, as Bo- 
decker proved by a special experiment. A solution of copper 
was strongly reduced by the urine. Recently Fiirbringer f de- 
tected alkapton by all of the tests given by Bodecker in the 
urine of a man twenty-nine years old, who suffered from lung 
disease. This urine contained no sugar. 

§ 27. Ii^rosiTE. 

_ T r^TT r^ r/^ TT ^ T f Carbou 40-00 

Formula: €.H,A [C.H,,0,,] I Hydro-en Q-QQ 

Crystallized: €JI, A + 2H,a [0,H,,0,, + 4H0]. [oxygen 53-34 

100-00 

A. Presence. Inosite, until recently, was found only in the 
muscular tissue, but Cloetta recently found this remarkable 
carbo-hydrate in the lungs (together with uric acid, taurin, and 
leucin), very abundantly in the kidneys (together with cystin and 
hypoxanthin), in the spleen (with uric acid, hypoxanthin, and 
leucin), and in the liver (with uric acid). Cloetta and Neukomm 
were able to prove the presence of inosite with certainty in the 
urine of Bright' s disease ; on the other hand, it was not found in 

* Annal. d. Chem. u. Pharm., Band 117, p. 93. 
f Berliner klinisclie Wocliensclirift, 1875, No. 24. 



ABNORMAL CONSTITUENTS OF URINE. 115 

normal urine. "W. Miiller and Nenkomm found inosite in the 
brain. Neukomm ^ found it sometimes in considerable quan- 
tity in the kidneys as well as in diabetic urine, together with 
large amounts of sugar, while Vohl saw it occur gradually in a 
diabetic urine in the place of sugar. Yalentiner was able to 
separate inosite in considerable quantity from the voluntary 
muscles of drunkards. Inosite is, however, a not unusual con- 
stituent of plants also ; Vohl found it in unripe beans {Phaseo- 
his vulgaris), W. Gintl t found it in the leaves of the ash, and 
Marme states that he has found it in the juices of various 
plants. I found it myself in considerable quantity in the grape 
juice, in the leaf of the vine, in the must, and in wine. 

B. Microscopic Properties, Inosite forms for the most part 
cauliflower-like groups of crystals, but at times it occurs in 
single crystals which are three or four lines in length. The 
crystals belong to the klinorhombic system. (Funke, Taf. VI., 
fig. 6 ; 2^*^ Aufl., Taf. V, fig. 3.) 

C. Chemical Properties. Inosite loses its water of crystalliza- 
tion in the air, and melts at 210° C. Its taste is distinctly 
sweet ; it is easily soluble in water, and insoluble in ether and 
alcohol. 

1. Melted inosite solidifies when rapidly cooled to pointed 
crystals ; on slow cooling, on the other hand, it becomes a horny 
mass. 

2. Inosite does not yield alcohol when treated with yeast, 
but in contact with putrefying cheese it yields lactic and buty- 
ric acids. The variety of lactic acid which is formed here is 
paralactic, which yields, on oxidation with chromate of potas- 
sium and sulphuric acid, malonic acid. (Hilger.)J 

3. If a solution of inosite is evaporated with nitric acid on 
platinum almost to dryness, and the residue is moistened with 
a little ammonia and solution of chloride of calcium, and the 
mixture is again evaporated carefully to dryness, a vivid rose- 
red color arises which is apparent with even one milligram of 
Inosite. (Scherer.) The real sugars do not give this reaction. 

4. If inosite is heated with a solution of cupric tartrate in 
potassic hydrate no reduction takes place, as in the case of 

*Canstatt's Jahresber. 1859, II. Abtli., p. 91 u. 98. 
\ Chem. Centralbl. 1869, p. 230. 
:j:Annal. d. Chem., Band 160, p. 333. 



lie ANALYSIS OF THE URINE. 

grape sugar, but a green solution results, from which, after a 
time, a light greenish precipitate falls, while the fluid above be- 
comes blue again. If this is filtered off, and the filtrate boiled 
again, the same change of color is observed. (Cloetta.) 

5. Neutral acetate of lead does not precipitate a solution of 
inosite, but on the addition of subacetate of lead, on the con- 
trary, especially on heating, a transparent gelatinous precipi- 
tate occurs, which becomes white in a few moments, and exactly 
resembles paste. (Excellent means of separating inosite from 
animal and vegetable fluids.) 

6. If a fluid containing inosite is evaporated to a few drops 
in a porcelain dish, and a small drop of a solution of mercuric 
nitrate is then added, a yellow precipitate is soon formed. If 
this is spread out as much as possible on the edge of the dish, 
and again warmed with great care, there remains, as soon as the 
fluid is all evaporated, if too much of the reagent has not been 
added, first a whitish-yellow residue, which soon becomes more 
or less dark red, according to the amount of inosite present. 
The color disappears on cooling, but reappears again on gently 
heating. Uric acid, urea, starch, sugar of milk, mannite, glyco- 
coll, taurin, cystin, and glycogen do not give this reaction. 
Albumen is colored red, and sugar is colored black, therefore 
neither of these substances should be present. (Gallois.)" I 
have frequently made use of this reaction with the best result. 

To prepare the mercuric solution, one jDart of mercury is dis- 
solved in two parts of ordinary nitric acid, it is evaporated to 
one-half and treated with one and a half parts of water. After 
twenty-four hours the clear fluid is poured off from the basic 
salt. 

D. Detection. As mentioned above, inosite was found in the 
urine of Bright's disease as well as in that of diabetes. The 
urine to be tested for inosite, after any albumen present is first 
separated, is completely precipitated with sugar of lead solu- 
tion, filtered, and the warmed filtrate treated with subacetate of 
lead as long as any precipitate occurs. It is Avell to concentrate 
the urine to one-quarter of its bulk on the water bath before 
precipitation. The subacetate of lead precipitate, which con- 
tains the inosite combined with lead oxide, is collected after 

*Zeitschrift f. analyt. Chem., Baud 4, p. 264. 



ABNORMAL CONSTITUENTS OF URINE. II7 

twelve liours, and, after washing, is suspended in water and de- 
composed with sulphuretted hydrogen. After standing awhile 
a little uric acid first separates from the filtrate ; the fluid is 
filtered from it, then concentrated as much as possible, and 
while boiling treated with three or four times its volume of 
alcohol. If a heavy precipitate results which adheres to the 
bottom of the glass, the hot alcoholic solution is simply poured 
off, but if a flocculent non-adhesive precipitate occurs, the hot 
solution is filtered through a heated funnel and allowed to cool. 
If after twenty-four hours groups of inosite crystals have de- 
posited, they are filtered and washed with a little cold alcohol. 
In this case it is advisable to dissolve the precipitate obtained 
by the addition of the hot alcohol once more in as little boiling 
water as possible, and precipitate it a second time with three 
or four times its volume of alcohol, etc., in order to avoid any 
loss of inosite. If, however, no crystals of inosite have sepa- 
rated, ether is gradually added to the clear cold alcoholic filtrate, 
until a milky cloudiness results on shaking thoroughly, and it 
is then allowed to stand in the cold twenty-four hours. If too 
small an amount of ether has not been taken (an excess does 
no harm), almost all of the inosite present is separated in 
shining pearly leaflets. (Cooper, Lane.)"^ 

Inosite, however, appears to occur only very rarely in urine. 
Gallois investigated the urine of one hundred and two patients, 
but found inosite only seven times ; it was found five times in 
thirty cases of diabetes together with sugar in very variable 
amounts, and twice in twenty-five cases of albuminuria. 

§ 28. BiLiAEY Substances. 

Of the constituents of the bile, the biliary coloring matters 
as well as the biliary acids occur pathologically in the urine, 
especially in icterus, phosphorus poisoning, etc. The biliary 
acids have also been found at times in the urine in pneumonia 
without the biliary pigments having been discovered at the 
same time. In fatty degeneration of the kidneys cholesterin 
appears also to have been found in the urine. 

*Aiinal. d. Chem. u. Pharm., Band 117, p. 118. 



118 ANALYSIS OF TEE URINE. 



BILIAEY COLORING MATTERS.* 

A. Presence. The biliary coloring matters occur in the bile 
and biliary calculi in different modifications ; we meet with them 
also in the contents of the intestine and in the excrement. 
Pathologically, especially in the severer forms of icterus, they 
appear in all of the fluids of the body and may even pass over 
into the tissues. 

B. Preparation. Powdered gall-stones are freed from choles- 
terin and fat by treating them with ether ; the residue is then 
boiled with water and treated with dilute hydrochloric acid. 
After washing and drying, the dark brownish green mass is 
boiled with chloroform as long as it continues to take up any 
pigment. After the chloroform is distilled off, the residue 
which remains is treated with absolute alcohol, by which a 
brown pigment, bilifuscin, is removed, while the red pigment 
(bilirubin — cholepyrrhin) remains behind. To purify the 
bilirubin it is repeatedly washed with ether and alcohol, 
then dissolved in chloroform, the solution allowed to evapo- 
rate until the pigment begins to separate, when it is precipi- 
tated by the addition of alcohol. A green coloring matter, 
biliprasin, is then withdrawn by alcohol from the residue of 
the gall-stones which has been left by the chloroform ; this, after 
evaporation of the alcohol, remains behind, and may be purified 
by washing with ether and chloroform, and dissolving again in 
a very little cold alcohol. Finally, after this treatment of the 
gall-stones there remains a brown body, bilihumin, insoluble in 
water, alcohol, ether, chloroform and dilute acids. 

C. Chemical Properties. 

a. Bilirubin {Cholepyrr]iin),£]^x^cf^i [CaoH^sN^O,,]. Bilirubin, 
besides in the bile, is found in the urine in icterus, etc. It 
is without doubt identical with the hsematoidin crystals oc- 
curring in old extravasations of blood. (Hoppe-Seyler.)t If 
faintly acidified bile is directly shaken with chloroform, bili- 
rubin remains behind after the evaporation of the chloroform 
in microscopic red tables and prisms, belonging to the rhombic 

•"* Annal. d. Cliem. und Pliarm., Band 132, p. 323. Journal f. pr. Chem., Band 
104, p. 28, 193, and 401. 
f Handbucli d. pliysiol. Analyse, 3'° Aufl,, p. 203. 



ABNORMAL CONSTITUENTS OF URINE. 119 

system. It is obtained from gall-stones according to tlie above 
method, as an amorphous orange-colored powder. Bilirubin 
is insoluble in water, yery difficultly soluble in ether and alco- 
hol, but readily soluble in hot chloroform, benzole, and bisul- 
phide of carbon. The solutions even on considerable dilution 
still have a yellow color. 

1. An ammoniacal solution of bilirubin gives with chloride 
of calcium, chloride of barium, acetate and subacetate of lead, 
and nitrate of silver precipitates which are insoluble in chloro- 
form. 

2. An alkaline solution of bilii-ubin, treated with an equal 
volume of alcohol and then with a little concentrated commer- 
cial nitric acid, gives rise to a magnificent play of colors. The 
yellow color first changes to a green, then blue, violet, ruby red, 
and at last dirty yellow. If shaking is avoided in the perform- 
ance of this test, all of these colors appear in layers, one above 
the other. The play of colors also appears without the addi- 
tion of alcohol, but then a few drops of red fuming acid must 
be added to the nitric acid. The limit of the reaction first 
begins at a diliition of from seventy to eighty thousand. 

This reaction is very elegant and positive if a dilute solu- 
tion of bromine in alcohol or simple bromine water is added 
drop by drop to a solution of bilirubin in chloroform. (Maly.) 

Maly has prepared the final yellow end-product of this re- 
action, and named it choletelin. Choletelin, however, is not 
identical with urobilin or hydrobilirubin, as has been affirmed 
by some. (Maly.)^ 

Characteristic changes of the spectrum correspond to this 
color-reaction. If the color of the solution approaches the blue 
modification, a dark absorption band appears between the lines 
C and D, beginning somewhat nearer D and reaching to about 
midway between D and E. On dilution the band resolves into 
two rather indistinct bands, a and /?, which are separated by a 
narrow clear space situated nearer to D. In the further prog- 
ress of the reaction these lines gradually diminish in intensity, 
but remain apparent up to the beginning of the red modifica- 
tion. Almost at the same time with a and /5, but usually a 
little later, a third band, ;/, appears between b and F almost 

* Zeitsclirif t f. analjt. Chemie, Band 11, p. 353 ; ibid., Band 13, p. 336. 



120 AI^ALYSIS OF THE URINE. 

exactly bounded by tliis last line, increasing in distinctness in 
proportion as tlie former bands become paler, and attaining its 
greatest intensity toward the end of the reaction, but finally it 
also disappears as the action of the nitric acid progresses. It 
is interesting that this band, y, corresponds to the absorption 
band, y, of urobilin. (See Urobilin.) (Jaffe* and Fudakowski.)t 
3. A solution of bilirubin in an excess of sodic hydrate be- 
comes green when exposed to the air. Bilirubin, by taking up 
oxygen, becomes converted into biliverdin. (Maly.):|: 

b. Biliverdin, ^leHigNoOj [CgoHigNiOg]. Biliverdin occurs pro- 
bably in icteric urine, which has become green after long stand- 
ing. It dissolves in alcohol with a beautiful green color ; in 
water, ether, and chloroform it is insoluble. 

1. In alkalies biliverdin dissolves with a green color in con- 
tradistinction to biliprasin, which produces with alkalies a 
brown. On long standing of the alkaline solution biliverdin 
finally becomes converted into biliprasin. 

2. An alkaline solution of biliverdin reacts with nitric acid 
the same as bilirubin. The color first becomes blue, then vio- 
let, red, and lastly dirty yellow. 

Bilirubin and also biliverdin can be changed to urobilin 
(hydrobilirubin) on treatment with sodium amalgam. (Maly.) 

c. Biliprasin, €,61102^2^6 [C3jIo2N20]o]. Biliprasin occurs in 
small quantity in gall-stones. It also probably occurs in the 
bile of the ox and in icteric urine. 

1. Biliprasin is insoluble in water, ether, and chloroform. 
Alcohol dissolves it with a beautiful green color, which becomes 
brown on the addition of ammonia. (Distinction from biliver- 
din.) 

2. Biliprasin readily dissolves in alkalies. Dilute solutions 
have the same color as strongly pigmented icteric urine. (On 
the addition of an acid the brown color becomes green again. 
Distinction from bilifuscin.) When brown icteric urine on 
sj^ontaneous acidification, as well as after the addition of an 
acid, shows the same change of color, it must be concluded 
that biliprasin is present in preponderant amount. (Stadeler.) 



* Journ. f. pr. Cliem., Band 104, p. 401. 

f Zeitsclirift f . analyt. Cliem. , Band 8, p. 516. 

J Journ, f. pr. Cliem., Band 104, p. 34. 



ABIiOBJIAL CONSTITUENTS OF URINE, 121 

3. An alcoholic solution of biliprasin shows the same reac- 
tion with nitric acid as bilirubin and biliverdin, only the blue 
is very faint and indistinct. 

d. Bili/Kscin, G-iJIo^iN^Qi [CssHooNoOtj]. This brown pigment 
has been thus far fonnd only in small amount in human gall- 
stones. It dissolves in alcohol and potassic hydrate with a 
brown color ; it is precipitated from alkaline solutions in brown 
flocculi by hydrochloric acid. Bilifuscin behaves the same 
with nitric acid as the other pigments. 

D. Detection. A urine which contains biliary pigments in large 
amount is always strongly tinged deep brown, reddish brown, 
greenish brown, dark green, or grass green. It foams strongly 
on being shaken, and colors a piece of filter paper dipped into 
it yellow or greenish. 

1. The reaction for the biliary coloring matters, even when 
present in very small amount, is most easily obtained by pour- 
ing into a conical test glass about an inch of concentrated nitric 
acid, which has been somewhat decomposed by standing in the 
light, and then carefully covering it with a layer of the urine to 
be examined by means of a pipette. If biliary pigment is pres- 
ent, the play of colors begins at the point of contact of the two 
fluids with a beautiful green ring which gradually rises, and on 
its lower border a blue, violet, red, and finally yellow ring grad- 
ually appears. (Kiihne.) It is to be observed here, however, 
that all of these colors do not always occur ; violet and green, 
for the most part, are the most permanent, and the green which 
first occurs, is alone demonstrative of biliary pigment, since red 
and violet rings also occur with uroxanthin (indican) and its 
products of decomposition. (See Uroxanthin.) The presence of 
albumen by no means disturbs the reaction, since the albumen 
coagulated by nitric acid, usually carries down at the same time 
a portion of the pigment, and thus shows the reaction in the 
most beautiful manner. But at all events the nitric acid ought 
not to contain too much nitrous acid, since in this case the re- 
action runs a very rapid course, and the colors are rapidly de- 
stroyed. 

In order to avoid a possible confusion between bilirubin and 
indican, Yitali* performed the test for the biliary pigments 

* Jahresbericlit ii. d. Fortscliritte der Thierchemie, 1873, p. 149. 



122 ANALYSIS OF THE UBmE. 

with nitrate of potassium and dilute sulphuric acid. A single 
drop of a solution of nitrate of potassium and a few drops of 
sulphuric acid suffice to produce a beautiful green color in a 
urine containing only mere traces of bile. After a time the 
color disappears and becomes yellow at once, without having 
previously passed through red and blue. 

2. The slightest traces of bilirubin can finally be detected 
in urine, even when the above reaction fails, if large amounts 
of urine are successively shaken with chloroform, the urine ex- 
tracted being frequently poured off. The smallest amounts of 
bilirubin are taken up by the chloroform, and sink with it to 
the bottom, giving it a yellow color. The supernatant urine is 
then removed and the chloroform solution covered with a layer 
of nitric acid which contains nitrous acid. The reaction now 
takes place from above downward, and shows very brilliantly 
even with the smallest traces of bilirubin. Another part of the 
chloroform solution is allowed to evaporate in the air, and the 
residue is examined microscopically. If bilirubin is present, 
single reddish-yellow crystals will be readily discovered, which 
show the color reaction with nitric acid very beautifully under 
the microscope. The crystals readily dissolve in alkalies ; the 
solution becomes green on standing exposed to the air. 

If in this reaction the chloroform should not readily and 
quickly settle, the urine is evaporated to dryness on the water 
bath, the residue is extracted with water, filtered, washed, 
dried, and the filter cut into small pieces, and repeatedly ex- 
tracted with chloroform while warm. The golden-yellow solu- 
tion which is obtained is directly tested for bilirubin with nitric 
acid or bromine w^ater. Frequently traces of bilifuscin can 
still be obtained by boiling alcohol from the residue, which 
has been exhausted with chloroform. (Schwanda.)" 

It is not advisable to test an alcoholic solution for biliary 
pigments with nitric acid, since alcohol also, in the absence of 
biliary pigments, readily gives a similar play of colors, owing 
to the formation of hyponitric acid. Finally, if a urine to- 
gether with biliary coloring matter contains haemoglobin also, 
the former is precipitated with subacetate of lead, the washed 
precipitate is decomposed with carbonate of sodium, and the 
filtrate used for testing with nitric acid. 

* Zeitschrift f. analyt. Chem., Band 6, p. 501. 



ABNORMAL CONSTITUENTS OF URINE. 123 

3. Cases not rarely occur, however, where the specified re- 
actions for biliary coloring matters remain absent, even when 
quite large quantities of pigment are present. According to 
the investigations of Prussak,* continued fever has an influ- 
ence on the failure of the reaction ; and Huppert t believes 
that he has found that in such cases the urine contains no bili- 
rubin but only biliprasin. To detect the latter, according to 
Huppert, the following method is used : The urine is precipi- 
tated with milk of lime ; the precipitate is collected, and while 
still moist is put into a reagent glass, which is then half filled 
with absolute alcohol, and dilute sulphuric acid is added until 
the fluid, after shaking, has a distinct acid reaction. It is 
heated, the precipitate filtered off, and the filtrate heated to 
boiling. The greenish-yellow or yellowish-green color of the 
fluid then changes quickly to a beautiful dark green, if an ex- 
cess of sulphuric acid is present, this change taking place the 
sooner the more free acid there is. Under certain circum- 
stances not thoroughly investigated, however, the fluid at times, 
on continued boiling, becomes dark blue. 

But this method is not sufficient in all cases, since, according 
to rudakowski,J products of the oxidation of bilirubin, w^hich 
form compounds with lime only with difficulty, occur not in- 
frequently in icteric urines. In that case it is more accurate to 
precipitate with subacetate of lead or sugar of lead and ammo- 
nia, and decompose the washed precipitate with oxalic or sul- 
phuric acid. The aqueous oxalic acid solution is evaporated to 
dryness, the pigment is extracted from the residue with chloro- 
form, and the acid solution thus obtained is tested with the 
spectroscope. The absorption band, y, between b and F, de- 
scribed above under Bilirubin, will be perceived more or less 
dark and sharply defined, according to the concentration. Fre- 
quently this absorption band can be detected if the urine, after 
sufficient dilution, is examined directly with the spectroscope 
in a layer two cm. thick. 

Investigations by A. Heinsius and F. Campbell § have proved 
that the icteric urine in these cases contained only cholete- 

*Centralbl. f. d. med. Wissenscliaft.,lS67, p. 97. 
f Zeitschrift f. analyt. Chem., Band 6, p. 291 u. 498. 
i Zeitsclirif t f. analyt. Chem., Band 8, p. 516. 
§ Archiv der Physiologie, Band 4, p. 497. 



124 ANALYSIS OF THE JJBINE. 

lin, tlie final yellow product of oxidation, wliicli is formed in 
Gmelin's test, and consequently cannot give the well-known 
change of colors on the addition of nitric acid. The familiar 
spectral appearance which characterizes the end of Gmelin's 
reaction can be readily obtained, however, with such urine, 
especially after acidifying with hydrochloric acid. 

§ 29. BiLiAEY Acids. 

The basis of all of the acids occurring in bile is the non- 
nitrogenous cholic acid, €<,4H^o05 [CjgHsgOg + HO]. When pure it 
crystallizes in colorless shining tetrahedra, rarely in quadri- 
lateral octahedra. It is not contained in the bile as such, but 
is united with taurin as taurocholic acid and with glycocoll as 
glycocholic acid. 

If cholic acid is heated to 190"" or 200° C, or boiled for a long 
time with acids, it decomposes into dyslysin, ^gJIse^s [Cj^HseOc], 
and water. Dyslysin is insoluble in water and alcohol ; very 
slightly soluble in ether. On being boiled with an alcoholic 
solution of hydrate of potassium it becomes cholic acid again. 
The barium salt of cholic acid dissolves with much difiiculty in 
cold water, more easily in hot water, and very readily in alcohol. 

1. Taurocliolic acid, Q.^R.J^m, [05345^8,0,,]. This acid, oc- 
curring in the bile in combination with sodium, has not yet 
been obtained in a crystalline form. When not absolutely pure 
it forms a white, amorphous, very hygroscopic powder having 
an intensely bitter taste, readily soluble in alcohol and water, 
and insoluble in ether. The barium salt of taurocholic acid 
is readily soluble in water. If taurocholic acid is treated a 
long time with potassic hydrate at a boiling temperature, it 
decomposes into cholic acid, which combines with potassium, 
while taurin is set free ; if hydrochloric acid is used instead of 
hydrate of potassium, it splits up in the same manner; the 
cholic acid, however, is not separated as such, but is changed 
partially into dyslysin by the action of the hot hydrochloric 
acid. 

The separated taurin, 0,H,{^NO, [C4H.S2^0g], crystallizes in 
colorless, regular, six-sided prisms with four- and six-sided ter- 
minations. (Funke, Taf. Ill, fig. 4 ; 2 ° Aufl., Taf. V., fig. 1.) This 
body contains nitrogen, and is characterized by containing 



ABNORMAL CONSTITUENTS OF URINE. 125 

twenty-five per cent, of sulphur. Taurin is readily soluble in 
water, less readily in alcohol ; the solutions have a perfectly 
indifferent behavior toward vegetable colors. 

Taurin is most readily obtained by evaporating fresh ox-bile 
free from mucus with strong hydrochloric acid, when the dys- 
lysin, etc., separates. The chloride of sodium is allowed to 
crystallize from the strongly concentrated fluid, the mother 
liquor is evaporated somewhat further, and the taurin is preci- 
pitated by admixture with double its volume of strong alcohol. 
It is obtained pure in the form of beautiful large crystals by 
re crystallization from water. 

2. Glycocliolic add, G.eH^sNOe [CsJI^^^On + HO]. This occurs 
also in normal bile in combination with sodium. Glycocholic 
acid crystallizes in the form of very fine needles (Funke, Taf. 
lY., fig. 6 ; 2^^^ Aufl., Taf. VIIL, fig. 5), wherein it essentially differs 
from taurocholic acid. It is quite readily soluble in hot water 
and alcohol, but on the contrary is very slightly soluble in 
ether. It does not crystallize from the alcoholic solution, but 
separates as a resinous mass on evaporation ; if, however, the 
solution is mixed with water, it gradually separates in the crys- 
talline form on evaporation. The barium salt of glycocholic 
acid is readily soluble in water. By boiling with potassic hy- 
drate, baryta water, or hydrochloric acid, it suffers a similar 
decomposition as taurocholic acid, cholic acid or dyslysin being 
set free and glycocoll separated. 

GlycocoU, O^HsNOs [C4II5NO4], is formed by treating gluten 
with mineral acids, from monochloracetic acid by the action of 
ammonia, and finally from hippuric and uric acids by heating 
with hydrochloric acid ; from uric acid at a temperature of 160^ 
to 170'' C. Glycocoll forms colorless rhombic prisms (Funke, 
Taf. III., fig. 5 ; 2^^ Aufl., Taf. IV., fig. 1), which are hard and 
permanent in the air, and taste almost as sweet as cane sugar. 
This body contains nitrogen but no sulphur. 

A. Emmerling ^ has discovered a new method for the synthe- 
sis of glycocoll. If cyanogen gas is treated with concentrated 
hydriodic acid, glycocoll is formed according to the following 
reaction : 

2 (ON) + 5IH + 2H2O =0,H5N02 + NH J + 14. 

*Ber. d. d. chem. Gesellsch., Band 6, p. 1351. 



126 ANALYSIS OF THE URINE. 

Chemical Properties. — 1. All of tlie biliary acids when com- 
bined, as well as free cholic acid also, react in a peculiar char- 
acteristic manner with sulphuric acid and sugar, which distin- 
guishes them from the coloring matters, as well as from taurin 
and glycocoll. If the aqueous solution of any one of the biliary 
acids is treated with a few drops of a solution of sugar and then 
with concentrated sulphuric acid until the mixture has a tem- 
perature of 50° to 70° C, the fluid becomes colored a beautiful 
purj)le violet. (Pettenkofer.) Oleic acid and albumen give a 
similar reaction. 

To distinguish this from similar reactions which are obtained 
with albuminous bodies, oleic acid and amyl alcohol, the spec- 
tral appearances of the biliary acid reaction can be used. If the 
fluid is diluted, so that only the violet is absorbed, an absorption 
band on the line F and a second between D and E, nearer E, 
appear. In concentrated solutions only the second band can 
be seen. (L. Schenk.)^ 

Even the smallest traces of biliary acids can be detected by 
means of this reaction in the following manner : A few drops of 
the fluid to be tested are evajDorated to dryness on the water bath 
in a porcelain dish ; a small drop of a solution of sugar (one 
gram of sugar in half a liter of water) and an equally small drop 
of concentrated sulphuric acid are added to it. It is then heated 
a few minutes on the Avater bath, and the violet-red color soon 
forms on the edge. At this moment the dish is removed from 
the water bath and allowed to stand quietly, when the reaction 
will increase considerably in intensity. In this manner I have 
succeeded in detecting with absolute certainty, by the most 
beautiful reaction, one four-hundredth to one six-hundredth of 
a milligram of the sodium salt of the biliary acids. On heating 
on the water bath, the reaction occurs much more positively than 
by evaporating over a free flame, as recommended by Neukomm. 

2. A second very delicate reaction is the following: The 
biliary acid or salt is covered with a small amount of concen- 
trated sulphuric acid, moderately warmed, and then water is 
added. The resinous flakes which deposit are separated from 
the acid, washed a few times with water without completely 
removing the sulphuric acid, and gently heated in a porcelain 

* Jahresbericht ii. d. Fortscliritte d. TMerclicmie, Band 2, p. 232. 



ABNORMAL CONSTITUENTS OF URINE. 127 

disli until they become colored. Then the residue is taken up 
with a very little alcohol, and the green solution is evaporated 
with constant turning, so that the inner surface of the dish be- 
comes covered with a deep indigo-colored coating, even when 
only a very little acid has been used. If the biliary acids are 
mixed wdth foreign matters, or if the sulphuric acid is allowed 
to act a long time, or at too high a temperature, the coating of 
pigment appears green. 

According to my experience, however, this reaction, even 
with the modification proposed by Von Bogomoloff,"^ is far less 
delicate and accurate than Pettenkofer's. 

Detection. — 1. A portion of urine (300 to 500 cc.) is evaporated 
on the water bath almost to dryness, and the residue is ex- 
tracted with ordinary alcohol ; the alcoholic solution is evapo- 
rated again, and the residue extracted with absolute alcohol. 
The solution thus obtained, now tolerably poor in salts, is freed 
from alcohol, the residue is taken up with a little water, the so- 
lution treated with subacetate of lead, of which an excess is to 
be carefully avoided, and the precipitate, after standing about 
twelve hours, is collected, washed, and gently dried between blot- 
ting paper. In order to remove as much as possible of other 
substances mixed with the lead precipitate, the lead compound 
with the biliary acid is extracted with boiling alcohol, the solu- 
tion is evaporated to dryness after the addition of carbonate of 
sodium, and the residue is treated with absolute alcohol in 
order to obtain the sodium compound with the biliary acid. 
The sodium salt thus obtained always contains, in addition to 
the biliary acids, small amounts of a resinous constituent of the 
urine, which is colored brownish red by sulphuric acid, at times 
also pale blue or violet, and on heating, after the addition of 
sugar, reddish or yellowish brown. This color is seldom so 
deep as to conceal the biliary reaction ; but if this is found to 
be the case, after a preliminary trial, the biliary acid is once 
more precipitated from the aqueous solution by subacetate of 
lead, the precipitate is collected after standing awhile and 
decomposed, as above, with carbonate of sodium. Then two 
or three drops of a solution of sugar (one part of sugar to 
four parts of water) are added to the aqueous solution of the 

*Zeitsclir. f. analyt. Chem., Band 9, p. 148. 



128 ANALYSIS OF THE URINE. 

sodium compound made as concentrated as possible, and after- 
ward pure concentrated sulphuric acid, free from nitric and 
sulphurous acid, is added. Care is to be taken here that the 
temperature does not rise much above TO"" C. If biliary acids 
are present the fluid first becomes cloudy, then clear, and 
at the same time yellow, but shortly afterward it changes to a 
pale cherry-red, dark carmine-red, and at last beautiful purple 
yiolet. 

The test becomes considerably more delicate, if it is per- 
formed with the modification given above ; one four-hundredth 
of a milligram of the sodium salt of the biliary acid can be 
detected with absolute certainty by this procedure. The pres- 
ence of biliary acids can be considered as proved only when 
the fluid becomes colored not only red, but also distinctly 
purple violet. 

The biliary acids may frequently be successfully detected by 
the following very simple method : A piece of filter paper is 
dipped into the urine to be tested after a little cane sugar has 
been previously added, and then the paper is allowed to dry. 
If a drop of pure concentrated sulphuric acid is then placed on 
the paper by means of a glass rod, there appears in about a 
quarter of a minute a beautiful violet color which is quite 
distinct, especially with transmitted light. This method is, 
in fact, very delicate, so that three one-hundred-thousandths 
(0*00003) of a gram of biliary acid gives the reaction in a most 
beautiful manner. Normal urine does not give this reaction. 
If a large amount of cane sugar is present, a reddish or brown 
color, which, however, cannot be confounded with Pettenkofer's 
reaction, appears. (G. Strassburg.)^ 

2. According to Hoppe the urine is directly precipitated with 
subacetate of lead and a little ammonia, the precipitate washed 
with a little water, and then boiled with a,lcohol and filtered 
while hot. The alcoholic filtrate is treated with a few drops 
of sodic hydrate solution, evaporated to dryness, and the so- 
dium salt of the biliary acids extracted from the residue by 
boiling with absolute alcohol. The alcoholic solution is evapo- 
rated to a small volume, and treated in a closed flask with 
ether, by which the biliary salts are precipitated and often 

* Archiv der Physiologie, Band 4, p. 401. \ 



ABNORMAL CONSTITUENTS OF URINE. 129 

crystallize out after long standing. In tlie employment of the 
test with sugar and sulphuric acid it is not necessary to wait, 
however, until the precipitate caused by ether has become 
crystalline, but the resinous precipitate dissolved in a little 
water can be immediately used for this purpose. If, however, 
we wish to determine whether cliolic acid is present in addition 
to giycocholic and taurocholic acids, the resinous precipitate is 
allowed to crystallize under ether, the ether is then poured off, 
the crystals dissolved in a little water and treated with a drop 
of chloride of barium solution. If a precipitate takes j)lace, 
the presence of cholic acid, whose barium salt is very difficultly 
soluble in water, is demonstrated. (Hoppe-Seyler.) 

3. According to Dragendorff, the biliary acids can be with- 
drawn from the urine by shaking w^ith chloroform. 120 to 150 
grams of urine are acidulated with a few drops of hydrochloric 
acid, and shaken with 30 grams of chloroform for at least an 
hour. The urine is separated by decanting, and the chloroform, 
which is colored brown by the precipitation of the extractive 
and coloring matters, is treated with six to eight cc. of absolute 
alcohol, which takes up the cloudy flakes while the chloro- 
form becomes perfectly clear again. It is then filtered, when a 
thick jelly frequently forms on the filter which contains the 
chloroform, and allows nothing more to flow through. If this 
jelly is detached from the filter, however, by stirring with a glass 
rod, the chloroform and alcohol pass through rapidly. The 
chloroform separated from the alcohol is then allowed to 
evaporate on watch glasses, and the residue is used for the 
test with sugar and sulphuric acid. By this method Yogel* 
found biliary acids in the urine of eight different healthy per- 
sons. To decide the question whether biliary acids really 
belong to the normal constituents of urine, Dragendorff then 
examined 1,000 cc. of the urine of each of ten healthy persons, 
varying in age from eight to fifty-five years, by the method 
given above under Detection. The sodium salt of the biliary 
acid which remained after the evaporation of the alcoholic solu- 
tion was dissolved in acidulated water, and the free biliary acid 
transferred to chloroform by shaking with it. The residue 
which remains after evaporation of the chloroform serves for 

* Zeitsclirif t f. analyt. Chem,, Band 11, p. 4G7. 



130 ANALYSIS OF THE UEINE. 

Pettenkofer's test. By working with one hundred liters of nor- 
mal urine, according to the method given, Dragendorff suc- 
ceeded in pre|)aring the biliary acids in pure form ; a part 
separated as the sodium salt of the biliary acids in microscopic 
crystals, and the elementary analysis gave corresponding re- 
sults. Dragendorff obtained from one hundred liters of normal 
urine O'T to 0*8 gram of biliary acids. 

It is always advisable to take large quantities of urine for 
working, since always only very small amounts of the biliary 
acids go over into the urine, even when the icterus is very 
intense. 

Cholesterin has sometimes been found in the urine in fatty 
degeneration of the kidneys, mixed with other fats. The sedi- 
ment, consisting chiefly of fat globules, was collected, dried on 
a water bath, and digested with a mixture of alcohol and ether. 
The filtered and concentrated extract deposited crystallized 
cholesterin, which, on account of its microscopic form, is not 
readily confounded with any other substance. (Funke, Taf. YL, 

If a little cholesterin is dissolved in about two cc. of chloro- 
form, and then about an equal volume of concentrated sul- 
phuric acid is added and the fluid shaken, the chloroform 
solution becomes rapidly colored blood red, and then beautiful 
cherry red or purple, a color which remains unchanged for 
days. The sulphuric acid, standing under the chloroform at 
the same time, has a strong green fluorescence. If some of the 
chloroform solution is poured into a saucer, it rapidly becomes 
blue, then green, and finally yellow, due to the absorption of 
water. (Salkowski.) The reaction is elegant and delicate. 

§ 30. Lactic Acid. 

■n 1 r^TTr. (Carbon 40-00 

Formula: €3H A Hydrogen 6-67 

L^e-tieUeJ ( Qxygen 53-33 

100-00 

A. Presence. Ordinary lactic acid from fermentation occurs 
partly free, partly in combination, in the juices of the stomach 
and contents of the intestine, and in fermenting diabetic urine 



ABNORMAL CONSTITUENTS OF URINE. 131 

as well as in sour milk. Paralactic acid occurs in tlie muscular 
juice of man and animals, in tlie bile, as well as very abundantly 
in the urine after phosphorus poisoning.^ It has also been 
found in the urine in acute atrophy of the liver, t trichinosis,:]: 
and osteomalacia. § Whether the lactic acid contained in dif- 
ferent glandular fluids and transudations is ordinary or para- 
lactic acid, requires still more accurate investigations. 

Lehmann has found that when the excretion of oxalate of 
calcium and uric acid is increased, lactic acid is always found 
in the urine. 

Hoppe-Seyler obtained lactic acid, together with brenzcate- 
chin, by the action of alkalies on sugar. 

According to the investigations of "Wislicenus,!! the lactic 
acid of flesh is a mixture of two different acids, the principal 
one of which turns the plane of polarized light toward the 
right, and forms well-cry stallizable salts, while the second acid 
occurs in less amount and jDossesses only a slight power of 
crystallization. Wislicenus found this second acid in ordinary 
meat in greater amount than in Liebig's meat extract, and in 
still greater relative amount in various pathological fluids of the 
animal and human body, such as urine, ascitic fluid, bile, etc. 
The optically active lactic acid of meat yields on oxidation with 
chromic acid no malonic acid; it is not, therefore, ethylen- 
lactic acid, with which the second is probably identical, which 
does yield malonic acid together with carbonic and oxalic acids 
on being oxidized with chromic acid. 

B. Chemical Properties. In the pure concentrated condition 
lactic acid is a colorless and odorless syrupy fluid, which hith- 
erto has never been crystallized, and has a strongly acid taste. 
It is soluble in water, alcohol, and ether, and attracts water 
from the air. At 140° it becomes free from water; but at a 
higher temperature it splits up into lactid, carbonic acid, and 
other compounds. 

There are no characteristic tests for lactic acid, but the 

* O. Scliultzen u. L. Eiess : Ueber acute Phospliorvergiftung und acute 
LeberatropMe. 

t Ibid. X Bericbte d. deutsch. cbem. Gesellsch., 1871, Heft 3. 

§ Moers u. Muck : Deutsclies Arcbiv f . klin. Med, , Band 5, p. 485. 

I Annal. d. Cbem. und Pharm. 167, p. 346. Tagblatt der 46 Versammlung 
deutsch. Naturforsclier u. Aerzte, Wiesbaden. 



232 Al^ALYSIS OF THE UBINE.. 

microscopic appearance of some of its salts is distinctive and 
very important for its recognition. 

1. Lactate of Calcium. This is formed by dissolving carbo- 
nate of calcium in lactic acid. It crystallizes under the micro- 
scope in fine needles collected in tufts. Of these tufts two are 
always so placed with their pedicles toward each other that 
they resemble pencils which run into each other. (Funke, Taf. 
IL, fig. l;2^«Aufl., Taf. I., fig. 4) 

Ordinary lactate of calcium contains 29-22 per cent, of water 
of crystallization, while paralactate of calcium contains 24*83 
per cent. 

2. Lactate of Zinc. This is formed by boiling pure oxide of 
zinc with lactic acid. The crystals, when separated rapidly 
under the microscope, appear in the form of spherical groups 
of needles, and may be readily obtained in great beauty. If, 
however, we allow a drop of a solution of lactate of zinc to eva- 
porate gradually, the crystals first appear club-shaped, trun- 
cated at both ends. These crystals gradually increase, the 
ends become smaller, while the middle becomes bellied. This 
peculiar bellied, barreled, or clubbed shape is very distinctive 
and characteristic of lactate of zinc. (Funke, Taf. II. ; 2^^ Aufl., 
Taf. L, fig. 5.) 

Ordinary lactate of zinc contains 18*18 per cent, of water of 
crystallization; paralactate, however, contains 12*90 per cent. 

C. Detection. The urine, which must be fresh, is evaporated 
almost to dryness on the water bath, and the residue treated 
with an alcoholic solution of oxalic acid. The oxalates which 
are thus formed, as well as the oxalate of urea, remain undis- 
solved, Avhile the lactic acid, together with the phosphoric and 
hydrochloric acids, are in solution. The fluid is digested with 
hydrate of lead, evaporated to dryness, and the residue extracted* 
with absolute alcohol which will dissolve the lactate of lead. 
The filtrate is treated with sulphuretted hydrogen, after filter- 
ing evaporated on the water bath to a syrup, and shaken with 
ether, which, after evaporation, leaves the lactic acid more or 
less pure. This is dissolved in a little water, boiled with zinc- 
oxide, filtered, and allowed to crystallize gradually on an object 
glass. The lactate of zinc is readily recognized by its barrel 
and club-shaped crystals, especially those which increase in 



size. 



ABNORMAL CONSTITUENTS OF UPJNE. 133 

Sclierer uses tlie following method for detecting lactic acid, 
wliicli yields excellent results in every way : The extract which 
is to be tested for lactic acid is dissolved in water, precipitated 
with baryta water, and filtered. Any volatile acids present are 
removed from the filtrate by distillation with a little sulphuric 
acid, and the residue is allowed to stand several days with 
strong alcohol. The acid fluid is evaporated with a little milk 
of lime to dryness, the residue is dissolved in hot water, and 
while still warm is filtered from the excess of lime and sulphate 
of calcium, a stream of carbonic anhydride is conducted into 
the filtrate, it is heated again to boiling, filtered from the pre- 
cipitated carbonate of calcium, the fluid evaporated to dryness, 
the residue warmed with strong alcohol, filtered if necessary, 
and the neutral filtrate set aside for a few days for the lactate of 
calcium to separate. If so little lactic acid is present that no 
crystals separate, it is evaporated to a syrup, mixed with strong 
alcohol and allowed to stand, when a usually dark deposit of 
extractive matter and lime is formed. The fluid is then poured 
into a closed vessel, and a small amount of ether is gradually 
added. Even traces of lactate of calcium, which can be readily 
recognized under the microscope, separate. 

Large amounts of lactic acid, such as occur in the urine after 
phosphorus poisoning, are separated in the following manner : 
The urine is strongly concentrated on the water bath, and then 
completely precipitated while warm with 95 per cent, alcohol. 
After twenty-four hours the clear alcoholic solution is decanted 
from the sediment, evaporated to a syrup, acidified with dilute 
sulphuric acid, and shaken with renewed quantities of ether as 
long as it takes up anything. After distilling off the ether the 
residue is dissolved in water, filtered, precipitated with sugar 
of lead solution, filtered, the filtrate treated with sulphuretted 
hydrogen, filtered again, and the acetic acid expelled by repeated 
evaporation on the water bath. The colorless fluid thus obtained 
is saturated with carbonate of barium, filtered, evaporated to a 
syrup, and the lactate of barium precipitated with absolute 
alcohol The mass, which is at first doughy, is changed into a 
granular crystalline powder by continued digestion with abso- 
lute alcohol, and its aqueous solution is accurately precipitated 
with sulphate of zinc, so as to form lactate of zinc. The zinc 
salt after evaporation separates from the filtrate in crystals 



134 ANALYSIS OF TEE URINE. 

with 12*9 per cent, of water of crystallization, and 26 '74 per cent, 
of zinc." 

§ 31. Volatile Fatty Acids. 

Of the volatile fatty acids there have thus far been found 
in the urine formic, acetic, propionic, butyric, and yalerianic 
acids. 

I. Formic Acid, GHgOo [C0H4O4]. Formic acid, besides in ants, 
occurs also in the poison-organs and stings of certain insects. 
It was, moreover, found in the sweat, in the fluid of the spleen, 
pancreas, thymus gland, muscles, and brain. Finally it occurs 
in the blood as well as in the urine, according to Buliginsky t 
and Thudichum.l It is formed by the decomposition of the 
coloring matter of the blood by acids ; also, according to Thudi- 
chum, by the decomposition of urochrom. Somewhat larger 
amounts of formic acid appear to occur in the urine of leukae- 
mia. (E. Salkowski.) 

Chemical Properties. Pure formic acid is a colorless fluid of 
intense piercing odor, which freezes at 0°, boils at 100^ C, and 
mixes with water and alcohol in every proportion. 

1. Ferric chloride causes a blood-red color in neutral solu- 
tions of formiates. 

2. Nitrate of silver does not precipitate free formic acid ; it 
preciiDitates formiates only when in concentrated solutions. For- 
miate of silver becomes black in the cold; on heating complete 
reduction immediately takes place. This reduction, in which 
the fluid is colored black, takes place even when the solution is 
so dilute that no precipitate occurs, or when free formic acid is 
present. 

3. If a solution of formic acid or one of an alkaline formiate 
is treated with mercuric chloride, and heated to 60° or 70° C, 
mercurous chloride (calomel) separates, and after more pro- 
longed boiling the metal also. Free hydrochloric acid prevents 
this reaction. 

4 On heating with concentrated sulphuric acid formic acid 
decomposes into carbonic oxide and water. 

* O. Scliultzen and L. Riess, loc, cit. 

f Hoppe-Seyler, Med. cliem. Mittlieilungen, Heft 2, p. 340. 

X The Journ. of the Chemical Society, vol. 8, p. 400, 



ABNORMAL CONSTITUENTS OF URINE. I35 

n. Acetic Acid, O.H^On [C4II4O4]. Acetic acid appears in the 
urine as soon as it has commenced to ferment. It also occurs 
in quite an amount during the fermentation of diabetic urine. 
It has been found also in muscular juice and in the fluid of the 
spleen, in leuksemic blood, in the contents of the stomach and 
vomitus together with free lactic acid in cases of disturbed 
digestion, in the sweat, and in the bile. According to Thudi- 
chum, acetic acid is also a product of the decomposition of 
urochrom. 

Chemical Projoerties. In the concentrated state acetic acid is 
a colorless fluid with an intensely acid smell and a sharp caus- 
tic taste, whose boiling point is 119" C. At 5° C. it crystallizes ; 
above 16^ C, however, it is fluid. Acetate of sodium crystal- 
lizes readily. 

1. Ferric chloride gives in solutions of an acetate a blood-red 
color of acetate of iron. 

2. Nitrate of silver gives in neutral solutions of an acetate a 
white crystalline precipitate of acetate of silver, which dissolves 
in hot water without reduction, and on cooling crystallizes out 
again. 

3. On heating an acetate with alcohol and sulphuric acid the 
characteristic odor of acetic ether is evolved ; with sulphu- 
ric acid alone the piercing odor of acetic acid is obtained. 

Crystallized acetate of sodium contains 22 '9 per cent, of so- 
dium, the barium salt 53*8 per cent, of barium, the silver salt 
64*67 per cent, of silver. 

HI. Propionic Acid, OaHgOo [0^11604]. Propionic acid is said 
to occur in the fluids of certain glands, in the sweat, in the gas- 
tric juice, in the vomitus in cholera, and in fermenting diabetic 
urine as well as in the bile. Salkowski^ mentions that he has 
found it also in normal urine. 

Chemical Projoerties, The concentrated acid is a colorless oily 
fluid, which boils at 138" C, has a peculiar odor and is readily 
soluble in water. The addition of a large amount of chloride 
of calcium separates it from its aqueous solution as an oily 
fluid. 

1. Nitrate of silver gives in concentrated solutions of propio- 
nates a whitish precipitate, which is soluble with partial reduc- 

« ArcMv d. Physiolog., Band 2, p. 361. 



136 ANALYSIS OF THE URINE. 

tion in boiling water. "When the solution cools the propionate 
of silver crystallizes in white, shining, microscojDic rosettes of 
needles. 

2. The propionate of barium is readily soluble in water, and 
crystallizes in octahedral prisms with oblique terminal surfaces. 

Propionate of silver contains 59*67 per cent, of silver, and 
the barium salt 48 '41 per cent, of barium. 

IV. Butyric Acid, ^411^02 [CsHsOj]. Butyric acid occurs in 
the sweat, in the contents of the stomach and in the vomitus in 
disturbances of the digestion, in the contents of the large intes- 
tine, in the solid excrement, and in the urine. It has also been 
found in the blood, juice of the spleen, contents of ovarian cysts 
and in the muscular juice. Lehmann found it at times in the 
urine of pregnant women, but also in that of women not preg- 
nant ; he has also frequently found butyric acid in the urine of 
men. 

If diabetic urine is treated with powdered chalk, and the 
mixture is allowed to ferment at a temperature of 35° to 40^ C, 
a considerable amount of butyric acid forms (Scherer, written 
communication), while at a lower temperature, without the 
addition of chalk, it often contains only acetic acid. 

Chemical Properties. The pure acid is an oily, colorless jfluid, 
which smells very disagreeably like rancid butter, and which 
boils at 157^ C. It is soluble in all proportions in water, alco- 
hol, and ether. Chloride of calcium separates it from the con- 
centrated aqueous solution as an oily layer of fluid. 

Most of the salts of butyric acid are soluble in alcohol and 
water, and on the addition of mineral acids develop the disa- 
greeable odor. 

1. Butyric acid forms compounds with the alkalies, alkaline 
earths, and the true metallic oxides. The compounds with the 
alkalies are deliquescent and uncrystallizable, while the other 
salts can be readily obtained in a crystalline form. 

a. Butyrate of Barium. This can be produced by saturating 
butyric acid with baryta water. If the compound is crystallized 
rapidly from such a solution it separates in the form of a pellicle 
shining like fat on the surface of the fluid, and appears under 
the microscope mostly in the form of close heaps of crystalline 
plates not accurately distinguishable. If, however, the solution 
of butyrate of barium is allowed to evaporate spontaneously, long, 



ABNORMAL CONSTITUENTS OF UrjNE. 137 

flattened, completely transparent prisms form, wliich lie together 
for the most part in stellate rosettes. This salt dissolves readily 
in water ; the solution blues reddened litmus paper. (Funke, 
Taf. I., fig. 8 ; 2^^ Aufl., Taf. IL, fig. 2.) Butyrate of barium con- 
tains 44*05 per cent, of barium. 

b. Metallic Butyrates are formed by precipitating a concen- 
trated solution of the butyrate of an alkali with the solutions of 
the various metallic oxides. Thus the nitrate of silver produces 
a yellowish-white crystalline precipitate of butyrate of silver, 
which is almost insoluble in cold w^ater and contains 55 "38 per 
cent, of metallic silver. 

V. Baldrianic Acid, GsHjoOo [OioHioOJ. Baldrianic acid has 
been found in the urine in typhoid fever, variola, and acute 
atrophy of the liver. It is formed very abundantly by the 
putrefaction of impure leucin in contact Avith ammonia. 

Chemical Properties. The pure acid is a colorless, oily fluid 
of penetrating odor, which boils at 175° C, and is readily soluble 
in alcohol and ether. It requires thirty parts of water, how- 
ever, to dissolve it. 

1. The baldrianates of the alkalies are easily soluble and not 
crystallizable, the other salts crystallize in shining crystalline 
scales. 

a. Baldrianate of barium crystallizes either in transparent 
prisms which disappear at 20° to 25° C, or more frequently in 
plates similar to those of cholesterin, which are readily soluble 
in water, but difficultly soluble in alcohol. This salt contains 
40 '41 per cent, of barium. 

b. Baldrianate of silver crystallizes in fine plates which shine 
like silver, and are difficultly soluble. It contains 51*67 per 
cent, of silver. 

Detection of the Fatty Acids. To separate the volatile fatty 
acids, as large an amount of urine as possible must be used. It 
is strongly acidulated with phosphoric acid, and then distilled 
as long as the distillate shows any traces of an acid reaction. 
If the residue in the retort becomes too concentrated, it is 
allowed to cool, water is added, and the distillation commenced 
anew. The different distillates are then united, saturated with 
carbonate of sodium, and evaporated to dryness. The residue 
is extracted with absolute alcohol, filtered, the filtrate evapo- 
rated to dryness, and the saline residue now obtained after the 



138 ANALYSIS OF THE UIUNE. 

addition of phosphoric acid, is subjected to distillation as long 
as the fluid which passes over has an acid reaction. The dis- 
tillate is first tested Avith nitrate of silver or mercuric chloride 
for formic acid. If this is present, it is destroyed by boiling 
with mercuric oxide, the fluid is saturated with carbonate of 
sodium, filtered, evaporated, and allowed to stand for a time to 
crystallize. If acetic acid is present, the acetate of sodium 
soon crystallizes, as, for example, in old diabetic urine, from 
which it separates abundantly, and is easy to recognize as 
such. If the acetate of sodium has separated, the mother 
liquor is acidulated again with phosphoric acid and subjected 
anew to distillation. The distillate which is now obtained is 
treated with baryta water in excess, carbonic acid is conducted 
into it until it has a neutral reaction, it is heated to boiling, 
filtered, and evaporated to a small volume for crystallization. 
The propionate of barium is the most soluble of the barium 
salts, the butyrate is the least soluble. Analysis of the barium 
salt obtained will give information of the nature of the acid if 
only one of the higher members is present, but if several are 
present at the same time, several barium salts must be obtained 
by fractional crystallization, and the amount of barium con- 
tained in each must be determined, since the material at hand 
would probably never suffice for producing the different acids 
in a state of purity. 

In using large amounts of urine benzoic acid also is almost al- 
ways obtained in the distillate, due to the decomposition of the 
hippuric acid. It sej^arates especially during the second distil- 
lation in crystalline plates, which remain partly adhering to the 
condenser and partly floating on the surface of the distillate, 
and can readily be recognized as such. 

§ 32. Benzoic Acid. 

Formula: G.HeO^ f ^J^^^^^^ ^^'^^ 

CuHeO, 1 Hydrogen 4-92 

I Oxygen 26*23 

100-00 

A. Presence. Benzoic acid occurs in the urine of herbivora 
probably after hard work or after wretched fodder. It is formed 



ABNORMAL CONSTITUENTS OF URINE. 139 

constantly in tlie putrefying urine of these animals, as well as 
in that of human beings, where it is formed by the decomposi- 
tion of hippuric acid. Benzoic acid is the non-nitrogenous 
component of hi^^puric acid, for, as we have seen above, benzoic 
acid in the economy takes up the elements of glycocoU and ap- 
pears again in the urine as hippuric acid. Conversely hippuric 
acid in contact with putrefying matters is decomposed imme- 
diately into benzoic acid and glycocoll again. Moreover, benzoic 
acid occurs as a product of the decomposition of many animal 
substances, especially protein bodies, gluten, etc. Hilger found 
in the urine passed after partaking largely of asparagus, benzoic 
acid together with hippuric acid, succinic acid, and an increased 
amount of ammonium salts. 

B. Mici'oscopic Properties. Sublimed benzoic acid appears in 
the form of colorless, fine, shining needles and leaflets, while 
that obtained from its solutions is in scales, small prisms, or 
six-sided needles, whose primitive form is a right rhombic 
prism. On cooling aqueous solutions, the crystals appear un- 
der the microscope always connected together, sometimes also 
in tables of exactly 90° overlapping each other ; in rare cases, 
one angle becomes truncated, but in such a way that the two 
angles are 135°. (Funke, Taf. I., fig. 6; 2'^ Aufl., Taf. II., fig. 6.) 

C. Chemical Properties. At 240° C. benzoic acid sublimes un- 
decomposed, its vapors irritate the throat and excite cough- 
ing. It is difficultly soluble in cold water, more easily in hot 
water; alcohol and ether take it up with tolerable ease. Its 
solutions redden litmus. Benzoic acid volatilizes with aqueous 
vapor ; therefore, only neutral solutions can be concentrated by 
evaporation. 

1. The benzoates are mostly soluble in water, only those of 
the heavy metals are difficultly soluble. The alkaline ben- 
zoates dissolve in alcohol. 

2. Strong acids decompose benzoates when in solution with 
the separation of benzoic acid in white shining scales. 

3. Chloride of iron gives in a solution of alkaline benzoates 
a brownish-yellow precipitate of benzoate of iron, which is de- 
composed by ammonia with the separation of ferric hydrate 
and formation of benzoate of ammonium. Benzoate of iron 
treated with a little hydrochloric acid dissolves with the sepa- 
ration of benzoic acid. 



140 AJSTALYSIS OF TEE UBISB. 

4 Free benzoic acid in a mixture of alcohol, ammonia, and 
chloride of barium solution, causes as little precipitation as the 
alkaline benzoates. (Distinction from succinic acid.) 

5. If benzoic acid is evaporated with a little nitric acid by 
boiling in a small porcelain dish, an odor of bitter almonds or 
nitrobenzol is evolved when the residue is strongly heated. 

D. Detection. The neutralized urine is evaporated to the 
consistence of an extract, and this is extracted with alcohol; 
after evaporation of the alcohol, benzoic acid separates in crys- 
talline form on the addition of a stronger acid. If its amount 
is very small, so that no crystals are obtained in this manner, 
the mass is extracted with ether which is then left to sponta- 
neous evaporation ; benzoic acid is separated from the ethereal 
extract in a crystalline form by water. The crystals are exam- 
ined chemically and microscopically. If succinic acid should 
be present at the same time, the acids are converted into 
their barium salts, and these are treated with boiling alcohol. 
Succinate of barium thus remains behind undissolved, while 
benzoate and any hippurate of barium present are dissolved. 
Benzoate of barium remains after evaporating the hot filtered 
alcoholic solution, and the benzoic acid is readily separated 
from this by hydrochloric acid. If hippuric acid is present, it 
can be easily separated by treating with ether, which dissolves 
the benzoic acid very readily. 

If, moreover, decomposed urine is treated as given under 
the head of Detection of the Volatile Fatty Acids, § 31, at the 
end of the second distillation, especially when it is pushed a 
little further, white scales and leaflets will be observed, which 
for the most part remain in the condensing tube, and are 
readily recognized as benzoic acid. 

§ 33. Fats. 

A. Presence. Urine containing fat is not a very frequent ap- 
pearance. The peculiar milky urine which sometimes occurs 
{urina cliylosa), frequently owes its cloudiness and color not to 
fat which is in suspension, but, as Lehmann declares, to a large 
number of pus corpuscles ; but Beale records a case of milky 
urine abounding in fat which was passed for months in the 
morning by a woman fifty years old. This urine became per- 



ABNOBMAL CONSTITUENTS OF URINE. 141 

fectlj clear after shaking with ether. Quantitative estima- 
tion showed in 1,000 parts 13*9 grams of fat. Beale believes 
that the chylous character arose from a separation of chyle by 
the kidneys. Beale found cholesterin also in the fatty cells 
passed with the urine in fatty degeneration of the kidneys, 
which, dissolved in other fats, could be obtained by first ex- 
tracting with alcohol and subsequent crystallization. Galac- 
turia appears to occur with special frequency in certain tropical 
regions. A series of cases is recorded in Schmidt's Jahrbuch, 
1863, 12, p. 274 

Eggel* records a similar case of chyluria. 390 cc. of this 
urine resembling milk yielded to ether 2*68 grams of fatty 
substance, in which the fatty acids, that is, neutral fats, choles- 
terin (?) and lecithin or the products of their decomposition, 
neurin and phosphoric acid, were detected. 

B. Microscojoic ProiJerties. Free fat is readily recognized un- 
der the microscope. With regard to the fat drops, they appear 
as flat disks, which possess a very great refractive power ; they 
have dark, tolerably irregular contours. The single dro^DS are 
frequently seen under the microscope to flow together, where- 
by they may be distinguished from fat cells which are per- 
fectly spherical. Fat cells have a round, smooth, sometimes 
polyhedral form from mutual pressure. The surface also has a 
strong refractive power; with transmitted light the contours 
are sharp and dark, but when examined by reflected light the 
borders appear shining like silver and the centre of the cells 
is whitish. It is easy to burst such cells by pressure, their 
contents then flow out, and the surface assumes a more or less 
wrinkled appearance. (Funke, Taf. YII., fig. 3 und 4 ; 2"" Aufl., 
Taf. XIV., fig. 3 und 4.) 

C. Detection. Since fat occurs in urine only rarely, and also 
only in very small amount, we naturally do not think of a 
separation and individual recognition of the different com- 
pounds, and must content ourselves with finding and recogniz- 
ing it as such. The microscopic appearance is so characteristic 
and significant that every one who has once seen a fat drop 
will recognize it again at the first glance. Our first attempt, 
therefore, is always to recognize under the microscope the 



* Centralblatt f . d. med. Wissenscliaft., 1870, p. 121. 



142 ANALYSIS OF THE URINE. 

above-mentioned qualities. If this does not succeed, a portion 
of the urine is evajDorated to dryness on the water bath, the 
residue is exposed for a time to a temperature of 110^ C, and 
is treated with successive small portions of ether as long as this 
takes up anything. This ethereal solution will now contain all 
the fat, and will leave it behind on evaporation, which is best 
performed in a small cylindrical glass. The residue can then 
be tested first microscopically and then chemically, as far as the 
material suffices. The production of greasy spots on fine paper, 
as well as the behavior on being heated (development of acro- 
lein), does not admit of a confusion with any other body. 

Chylous urine for the most part contains, in addition to greater 
or less amounts of fat, which is held in the form of an emulsion 
by the albumen present at the same time, lymph and blood 
corpuscles. A creamy layer frequently collects on the surface, 
and after a shorter or longer time fermentation occurs, when 
fibrinous coagula soluble in a solution of nitre separate. These 
fibrinous coagula are either delicate white, and fill the whole 
fluid, or they form clumps of a light or dark red color, some- 
times dense, sometimes delicate and mucus -like, which are 
also soluble in nitre."^ 

§ 34 SULPHUKETTED HYDROGEN. 

Sulphuretted hydrogen sometimes occurs in the urine, but 
only in rare cases. Its presence is readily recognized by the 
fact that a piece of paper moistened with a sugar of lead 
solution is blackened. The experiment is best performed in 
the following manner : A small beaker is half filled with the 
urine to be tested for sulphuretted hydrogen, and it is then 
covered with a watch glass, on the low^er surface of which a 
small piece of lead paper has been fastened by moistening with 
a drop of water. According to the amount of sulphuretted hy- 
drogen present, the paper will soon become brown or black, 
especially if the urine is slightly warmed. Sulj^huretted hydro- 
gen is also easily recognized by its stinking odor like that of 
rotten eggs. I have had the opportunity here of observing a 
specimen of urine which contained sulphuretted hydrogen for 

* Schmidt's Jahrbticlier, 1863, 12, p. 278. 



ABNORMAL CONSTITUENTS OF URINE. I43 

a long time, and which was passed periodically by a man whose 
lower extremities were paralyzed by gout ; the urine, when it con- 
tained sulphuretted hydrogen, was feebly acid, of bright yellow 
color, usually deposited a sediment, and immediately blackened 
very intensely a lead paper held over it. 

Betz assumes that under certain circumstances sulphide of 
ammonium from the intestine may get into the blood and then 
cause symptoms of poisoning, which are similar to those caused 
by the inhalation of sewer gas. Betz calls the sickness thus 
caused hydrothion-ammonsemia ; in the cases described by him 
the freshly passed urine gave for a long time the reactions of 
ammonia and sulphuretted hydrogen.^ 

It has been intimated above, under the head of Sulphuric 
Acid (§ 15, B, 3), that sulphates in contact with organic matters 
at a moderately elevated temperature may easily give rise to 
the formation of sulphuretted hydrogen, which is one source 
of this body in the urine. But sulphuretted hydrogen may be 
generated also without the presence of sulphates, by the simple 
putrefaction of animal matters containing sulphur, and thus it 
may happen that sulphuretted hydrogen can frequently be re- 
cognized by its odor in a urine which contains albumen after 
standing a short time, as I have had frequent opportunity of 
observing. 

E. Sertoli,t moreover, gives an account of a body precipita- 
ble by sugar of lead, soluble in ammonia, alcohol, and ether, 
decomposing with the evolution of sulphuretted hydrogen on 
being heated with dilute acids to 100° C, and which was found 
by him in the urine of horses, dogs, and human beings. It is 
easy to become assured of the presence of a body in the urine 
which contains sulphur, since the urine of men, horses, and 
dogs develops, on being treated with zinc and hydrochloric 
acid, sulphuretted hydrogen, which can be detected by the 
blackening of a strip of paper moistened with sugar of lead so- 
lution. For the quantitative estimation of the sulphur in the 
urine, which is not present in the form of sulphates, but 
in the form of this body which furnishes sulphuretted hydro- 
gen, the following method may be adopted : The uric acid is 



* Betz Memorabilien, 1864, p. 146. 

f Dair Istituto fisiolog. di Pavia, 1869. 



144 ANALYSIS OF THE URINE. 

precipitated from tlie urine of healthy persons and the fil- 
trate divided into two equal parts. In one half the sulphuric 
acid is directly estimated, in the other after it has been heated 
with hydrochloric acid and chlorate of potassium till chlorine 
is developed. From the difference in the amounts of sulphuric 
acid of the two estimations the amount of sulphur which was 
originally present not as sulphate is obtained. A twenty-four 
hours' amount of urine wdiich was 1,500 cc. gave 0'156 gram of 
sulphuric acid as the product of oxidation of the sulphur con- 
tained in the sulphur compound. (W. Lobisch.)"^ Finally it is 
to be remarked that Schmiedebergt and Meissner:]: have de- 
tected hyposulphurous acid as an almost constant constituent 
of the urine of cats and a very frequent constituent of the urine 
of dogs. 

§ 35. Allantgii^'. 





r Carbon 


30-38 


Formula : e.H.N^as 


Hydrogen 


3-80 


[C^HeN.O,] 1 


Nitrogen 


35-44 




- OxygeD 


30-38 



100-00 

A. Presence. AUantoin is found in the allantois fluid of the 
cow and in the urine of young calves as long as they are suckled 
or fed with milk. It is further found in the amniotic fluid, and 
in the urine of newborn children within the first eight days 
after birth. Stiideler found it in the urine of the dog when 
there was disturbance of the respiration ; Meissner and Joly 
also found it in dogs, together with succinate of sodium, after 
a continuous diet abounding in fat ; Kohler found it in the 
urine of the rabbit after the injection of oil into the lung. 
Schottin found it finally in human urine after large amounts of 
tannic acid had been taken. AUantoin is formed from uric acid 
by treating it with lead peroxide, ferrocyanide of potassium, or 
permanganate of potassium. 

B. Preparation. Uric acid is mixed to a thin paste with 

* Sitzungsbericlit d. wien. Acad., Band 63, II. 

f ArcWv d. Heilk. 1867, p. 422. 

X Zeitschrift fiir rat. Med. 1868, Band 31, p. 322. 



ABN0B3IAL CONSTITUENTS OF URINE. 145 

water, heated to boiling, and lead peroxide is added in small 
portions nntil the brown color of the latter no longer disap- 
pears. Allantoin separates from the filtrate on cooling in beau- 
tiful crystals, while urea remains dissolved in the mother 
liquor. 

C. 3Iicroscopic Properties. Allantoin appears under the micro- 
scope in perfectly clear, shining, colorless, prismatic crystals 
of a rhombic form, which, when obtained from concentrated so- 
lutions, unite into star-shaped rosettes. (Funke, Taf. Y., fig. 4; 
2- Aufl., Taf. III., fig. 4) 

D. Chemical Projoerties. Allantoin has no taste and does not 
act on vegetable coloring matters ; it is soluble in 160 parts of 
cold water, more readily soluble in hot water. Hot alcohol 
also takes it up, but it separates again for the most j)art on 
cooling. It is insoluble in ether. 

1. Concentrated alkalies decompose allantoin with absorp- 
tion of water into oxalic acid and ammonia. 

2. Boiling nitric acid splits it up into urea and allantoic acid. 

3. If nitrate of silver and ammonia are added to a saturated 
solution of allantoin, allantoin silver oxide precipitates in white 
flakes which, when examined microscopically, are seen to con- 
sist of clear perfectly spherical globes. The dry compound 
contains 40*75 per cent, of silver. 

4. Corrosive sublimate does not precipitate a solution of al- 
lantoin, but it is precipitated like urea by a solution of mercuric 
nitrate. 

5. Allantoin in contact with yeast at a temperature of 30° C. is 
decomposed into urea and oxalate and carbonate of ammonium. 
At the same time a new syrupy acid is formed, which is, per- 
haps, identical with one which I observed together with allan- 
toin and urea after treating uric acid with permanganate of 
potassium. 

E. Defection. To find allantoin the urine is precipitated with 
basic acetate of lead, filtered, and the excess of lead removed 
from the filtrate by sulphuretted hydrogen. The filtered so- 
lution is evaporated to dryness on the water bath, and the 
residue extracted with boiling dilute alcohol. After the cool- 
ing of the filtrate, concentrated by evaporation if necessary, if 
allantoin is present, crystals shoot forth which, after recrystal- 
lization from hot water, are to be further examined. Besides 

10 



146 AJS'ALYSIS OF THE URINE. 

the microscopic forms of pure allantoin, allantoin silver oxide 
(D, 3) is especially characterized under the microscope by its 
peculiar globular form. According to Meissner the following 
method is to be pursued : The urine is precipitated with baryta 
water, the excess of baryta is carefully removed with sulphuric 
acid avoiding an excess of the latter, and the alkaline filtrate 
treated with concentrated corrosive sublimate solution as long 
as a precipitate results. The mixture, wdiich has now become 
acid, is neutralized with potassic hydrate, aud further treated 
with corrosive sublimate solution. The collected precipitates 
are suspended in water and decomposed by sulphuretted hydro- 
gen. Allantoin separates from the concentrated filtrate in crys- 
tals. The allantoin Avhich is obtained is best crystallized once 
more from hot water, before the microscopic examination and 
production of the characteristic silver compound. 

The urine of young calves is evaporated to a syrup on the 
water bath and placed at rest for several days. The separated 
crystals are washed and then heated to boiling with a little 
water. The solution is decolorized by animal charcoal, filtered 
while hot, treated with a few drops of hydrochloric acid to pre- 
vent the separation of phosj^hate of magnesium, and allowed to 
cool, when allantoin will separate in thin bundles of coalescing 
crystals. 

The urine of calves, unlike that of full-grown creatures which 
no longer live on milk, is strongly acid ; it contains as much 
urea and uric acid as human urine, but no hippuric acid, Avhile, 
on the o\h.QY hand, cow's urine, which abounds in hippuric acid, 
contains no allantoin. 

APPENDIX. 

Alloxan. This interesting product of oxidation of uric acid 
(§ 6, D, 6 and 7) has thus far been found only once by Liebig* 
in a catarrhal intestinal mucus, and again probably by G. Lang t 
in the urine of a patient with heart disease. 

•'' Annalen d. Cliem. u. Pliarmacie, Band 121, p. 80. 

f Centralblatt f. med. Wissenscliaft., 1867, p. 63. Zeitsclirlft f. analyt. Chem., 
Band 6, p. 294. 



ABNORMAL CONSTITUENTS OF URINE. 147 



36. Leucin. 



Formula : CoHja^^Os 
[CH.aNOJ 



- Carbon 54-96 

Hydrogen 9-92 

Nitrogen 10-68 

. Oxygen 24-44 



100-00 



A. Presence. Leucin was first obtained as a product of the 
decomposition of animal matters abounding in nitrogen as well 
by tlieir putrefaction as by tlie action of strong acids and 
alkalies upon them, but very recently it lias been recognized 
as a normal and pathological constituent of various organs and 
fluids of men and animals, in which it often occurs jointly with 
tyrosin. According to the recent investigations of Kadziejewsky ^' 
leucin occurs normally in the pancreas, in the spleen, the lymph 
glands, salivary glands, in the thyroid and thymus glands and 
in the liver ; in the kidneys it is doubtful. It does not occur in 
the testicles, lungs, heart and other muscles, in the brain, blood, 
urine, saliva or bile. Leucin occurs pathologically in the urine 
in several diseases, tyj)hoid fever, small-pox, hepatic diseases, 
and is especially abundant together with tyrosin in acute atro- 
phy of the liver. V. Gorup-Besanez found leucin with asparagin 
in the juice of the embryo of the common vetch ( Vicia saiiva). 

B. Microscopic Properties. Impure leucin, as it is first obtained 
by separation from animal fluids, crystallizes in granular masses, 
which appear as round spheres, mostly yellow, in part concen- 
trically striped, here and there also covered with fine points, 
yet under the microscope showing no definite crystalline form, 
but frequently rather reminding one of spherical fat-cells. In 
the pure state it crystallizes in rosettes of leaflets or scales, 
whose contour is often difficult to distinguish. More frequently 
the edges are seen as sharp dark lines, so that at the first sight 
several crystals appear only as needles fine as hairs which 
terminate in two points. (Funke, Taf. III., fig. 6; 2''^ Aufl., Taf. 
IV., fig. 2.) 

C. Chemical Properties. — 1. Pure leucin forms white crystalline 

*Arcliiv f. patliolog. Anat., Band 36, p. 1, auch Zeitsclirift f. analyt. Cliem., 
Band 5, p. 466. 



148 AlfALTSTS OF THE URINE. 

scales, lias a greasy feel, and lias iieitlier taste nor odor. "Water 
moistens it with difficulty, but dissolves it with tolerable readi- 
ness ; in alcohol it is more difficultly soluble ; it is not at all 
soluble in ether. Acids and alkalies take it up with ease. 

2. Cautiously heated in a glass tube, open at both ends, to 
about 170^ C, leucin sublimes without previously melting in 
woolly flocculent masses, which fly about in the air like oxide of 
zinc partially borne along by the current of air. This inter- 
esting sublimation is very characteristic of leucin. On being 
strongly heated, 180° C, it melts and is decomposed into car- 
bonic acid and amylamin. 

3. If a boiling mixture of leucin and sugar of lead solution is 
carefully treated with ammonia, leucin lead oxide separates in 
beautiful iridescent leaflets. 

4 A solution of mercuric nitrate does not precipitate a solu- 
tion of absolutely pure leucin. If a precipitate is thus produced, 
it indicates, especially if the supernatant fluid is colored reddish 
or rose red, an admixture with tyrosin. 

5. Leucin in contact with putrefying animal matters or on 
being fused with potassic hydrate decomposes, with the forma- 
tion of carbonic acid, ammonia and hydrogen, into baldrianic 
acid. 

6. If pure leucin is carefully evaporated with nitric acid on 
platinum foil, a colorless, scarcely perceptible residue remains. 
If a few drops of sodic hydrate are added to this residue and 
heated, the leucin thus treated dissolves according to its purity 
to a perfectly colorless or more or less colored fluid. If this 
is carefully concentrated on the platinum foil over the lamp, in 
a short time it collects into an oily drop, which does not wet 
the platinum foil but rolls about without adhering to it. This 
appearance is very characteristic even for leucin not wholly 
pure. (Scherer.) 

7. Leucin in alkaline solution is decomposed by permanga- 
nate of potassium into ammonia, carbonic acid, oxalic acid, and 
baldrianic acid. 

8. If leucin is heated in a test tube with manganese dioxide 
and dilute sulphuric acid, the characteristic odor of valeronitrile 
is developed ; and if the oxidation is carried farther, especially 
if concentrated sulphuric acid is used, that of valerianic acid. 

D. Preparation and Detection. (See under Tyrosin.) 



ABKOBMAL CONSTITUENTS OF UBINE. 149 



§ 37. Tyeosin. 



Formula : OgHnNO, 

[CeH.NOe] 



Carbon 59-67 
Hydrogen 6-08 
Nitrogen 7*73 
Oxygen 26-52 



100-00 



A. Presence. Tyrosin is formed in just tlie same manner as 
leucin, only a little later, but for tlie most part together with 
it during the decomposition of animal matters abounding in 
nitrogen. Tyrosin never occurs normally in the organism, 
according to the thorough investigations of Eadziejewsky,^ but 
it does occur in the liver, in the blood of the hepatic and 
portal veins in diseases of the liver, in the bile of typhoid-fever 
patients, in the expectoration in croupous bronchial affections, 
etc. Leyden found it in the expectoration of a girl who had 
suffered ten years from a cough. It has been found in the 
urine in typhoid fever and small-pox, and in large quantity 
together with leucin in acute atrophy of the liver. (Frerichs, 
O. Schultzen, and L. Eiess.) 

B. Microscopic Propei^ties. Tyrosin forms a cohesive, snow- 
white mass which has a silky lustre and consists of long shining- 
needles lying together, which again are themselves formed of 
very fine needles arranged in star-shaped groups. It crystal- 
lizes from an ammoniacal solution often in globules, which con- 
sist of a number of fine needles radiating from the centre, and 
appear toothed on the entire periphery by the projection of 
small pointed crystals over the edge of the sphere. Such a 
tyrosin sphere on being crushed under the covering-glass crum- 
bles into fragments which consist of very fine white needles. 
(Scherer.) (Funke, 2^^ Aufl., Taf. IV., fig. 3.) 

C. Chemical Properties. Tyrosin is without taste and odor, 
very difficultly soluble in cold water, easily in hot, still more 
easily in acids and alkalies, but insoluble in alcohol and 
ether. 

* Loc. cit. 



150 AJSTALYSIS OF THE URINE. 

1. It evolves the odor of phenol and nitrobenzol on being 
heated. (Kiihne.) It is not capable of sublimation. 

2. Nitric acid evaporated carefully with tyrosin yields besides 
oxalic acid a yellow body which is the nitrate of nitrotyrosin ; 
this residue becomes colored a deep red-brown by potassic 
hydrate and ammonia. If tyrosin is evaporated with nitric 
acid (sp. gr. 1*2) on platinum foil, the rapidly soluble tyrosin 
becomes colored bright orange-yellow when first touched by 
the hot nitric acid. On evaporation it leaves a shining, trans- 
parent, deep yellow residue, and if a few drops of sodic hydrate 
are added to it, the fluid immediately becomes colored deep 
reddish yellow and on evaporation leaves an intense blackish- 
brown residue. Scherer prefers this reaction even to Piria's 
(4), because of its easy performance. 

3. If a boiling solution of tyrosin is treated with a solution 
of neutral mercuric nitrate, obtained by treating an excess of 
mercuric oxide with nitric acid, a yellowish- white voluminous 
precipitate results. If then a few drops of fuming nitric acid 
mixed with a large amount of water are added drop by drop to 
the fluid to be examined, which is allowed to boil anew after 
the addition of each drop, the whitish precipitate immediately 
becomes dark red. If the amount of tyrosin is very small, the 
fluid, which was before only turbid, like milk, becomes pale red, 
and after a time dark-red flocculi are deposited, while the fluid 
becomes colorless. (L. Meyer.) 

4. If a few drops of concentrated sulphuric acid are poured 
over tyrosin in a porcelain dish, it dissolves, on being gently 
heated, with a transitory red color. If then, after diluting 
with water, the acid is neutralized with a milk of carbonate of 
barium, boiled to destroy the bicarbonate of barium, and a dilute 
neutral solution of ferric chloride carefully added to the filtrate, 
a beautiful violet color is produced. No great amount of leucin 
should be mixed with the tyrosin. This reaction is very deli- 
cate ; the color appears bright rose-red in an ordinary test tube 
at a dilution of 6,000, in a layer two inches thick a distinct rose- 
red color is observed at a dilution of 25,000, and in one eight 
inches thick at a dilution of 45,000. (Piria, Stadeler.) 

D. Preparation. Two pounds of horn shavings are treated 
with a mixture of five pounds of English sulphuric acid and 
thirteen pounds of water, and boiled twenty-four hours consec- 



ABNOBMAL CONSTITUENTS OF URINE. 151 

utively, the water evaporated being renewed. The sulphuric 
acid is then removed by milk of lime, the mixture filtered, 
washed with hot water, and the filtrate, after the solution has 
been concentrated to about twelve pounds, is freed from dis- 
solved lime by the careful addition of oxalic acid. The filtrate 
is evaporated until a crystalline pellicle forms. The rosettes 
of crystals obtained consist of leucin with varying amounts of 
tyrosin, which is seldom absent. The different solubility of the 
two substances in water is utilized to separate them ; for this 
purpose they are dissolved in so much boiling water that on 
cooling only a small part of the crystals separate, which consist 
of white needles of the difficultly soluble tyrosin. Leucin is 
obtained from the mother liquor after previous decolorization 
with animal charcoal and further evaporation in white masses 
of crystals.* 

The following method of "W. Kiihne t is an excellent one : 
The pancreas of a well-nourished animal which has been abun- 
dantly fed five or six hours before death, is weighed while 
fresh, cut into pieces, triturated with water and sand to a fine 
mush, ten times its amount of raw blood fibrine is added, and 
the whole treated with twelve or fifteen parts of water, which 
should be previously warmed with the fibrine to 45^ C. The 
mass is kept at this temperature with frequent stirring for four 
or fiYQ, hours, then a little acetic acid is added, and it is heated 
to boiling. It is then strained through linen, the fluid is evapo- 
rated to a thin syrupy consistency, and while still hot is treated 
with strong alcohol and shaken in a flask until a distinct floccu- 
lent precipitate results. After cooling, this is filtered, and the 
filtrate is concentrated by evaporation until it forms a thick 
pulp when hot. After the mass has stood a day in the cold, it 
is freed as much as possible from the mother liquor on a filter, 
washed with a little cold water and then suspended in con- 
siderable water at about 50° C, when all of the leucin is dis- 
solved while the tyrosin remains behind nearly white. It is 
first re crystallized from hot water to purify it, and then from 
hydrochloric acid or ammonia to obtain large crystals. 

* Schwanert liber Leucin ; Dissertation, Gottingen, 1857. Stadeler. Annal. der 
Chemie und Pliarm., Band 116, p. 61. 

f ArcMv f. path. Anat., Band 39, p. 130. Zeitsclirift 1 analyt. Chemie, 
Band 6, p. 282. 



152 AJ^ALYSIS OF THE URINE. 

E. Detection. In acute atropliy of the liver under certain cir- 
cumstances only traces of those substances occurring normally 
as the final product of metamorphosis, especially urea, are 
found, while leucin and tyrosin occur as the principal constitu- 
ents. Such a urine often deposits a greenish-yellow sediment 
spontaneously, consisting of spherical rosettes of tyrosin nee- 
dles, and leaves a residue of numerous crystals of both sub- 
stances when it is evaporated on an object glass. To obtain 
larger amounts of both bodies Frerichs freed such a urine from 
the coloring and extractive matters, as it also gave distinct 
reactions for biliary pigments, by precipitating it with basic 
acetate of lead, immediately after obtaining it, with a catheter ; 
he then filtered, precipitated the excess of lead from the fil- 
trate by sulphuretted hydrogen, and concentrated the clear 
fluid. After twenty-four hours a sufficiently large amount of 
tyrosin had separated to suffice for several elementary analyses.'^ 
The tyrosin obtained is recrystallized from hot water and the 
chemical and microscopic tests are applied to it. To find leucin 
the evaporated residue is next treated with cold absolute alco- 
hol, as long as it takes up anything, and it is then extracted 
with boiling alcohol of ordinary strength, when a substance re- 
mains behind for the most part viscid, dark brown, soluble in 
water, and containing the remainder of the tyrosin. The alco- 
holic solution last obtained is evaporated and the syrupy resi- 
due allowed to stand a long time, when any leucin present 
separates in the globular form described above, § 36, B, and is 
to be subjected to microscopic and chemical examination. It 
is better, having first as much as possible freed the leucin ob- 
tained from its mother liquor by pressing between paper, to 
further purify it ; for which purpose its compound with lead 
oxide may be utilized. The aqueous solution of the leucin, 
which has been purified as much as possible by pressure, is 
made strongly alkaline with ammonia for this purpose and then 
precipitated with acetate or basic acetate of lead solution as 
long as a precipitate results. The precipitated leucin lead 
oxide is collected on a filter, washed a little, then suspended in 
water and decomposed with sulphuretted hydrogen. The fil- 

* Together witli tyrosin still another body crystallizing in a similar fomi 
was found, which contained more nitrogen (8 '83 percent). Frerichs, Deutsche 
Klinik, 1855, Nr. 31, p. 343. 



ABNORMAL CONSTITUENTS OF URINE. 153 

trate after evaporatioii will separate the leucin in pure crystal- 
line form. (Lelimann.) If the urine should contain albumen, it 
is first coagulated by heat, and the filtrate used for testing for 
leucin and tyrosin. 

It is to be remarked further that such a urine is to examined 
while fresh, since leucin in contact with decomposing animal 
matters is very readily decomposed with the formation of bal- 
drianic acid. 

The urine from the case of acute atrophy of the liver, described 
by Frerichs, contained 4*9 per cent, of solid residue and 0*14 
per cent, of ash. The residue was strongly acid, and urea was 
sought for in it in vain. He obtained, besides leucin and tyro- 
sin, a viscid substance, similar to that which is formed with 
leucin and tyrosin by the artificial decomposition of protein 
substances by acids. The ash consisted chiefly of chlorine com- 
pounds and sulphates ; it was remarkable that the alkaline and 
earthy phosphates were wholly wanting. These statements 
were partially confirmed by O. Schultzen and L. Eiess.^ 



§ 38. OXYMANDEL AciD. 

, r^. TT rx r Carbon 57*14 

da : 4^8ll8Q4 ) tt i ^ ^p 

rr H01 i Hydrogen 4-76 



100-00 



Presence. Oxymandel acid, was found by O. Schultzen and 
L. Eiess t in the urine in several cases of acute atrophy of the 
liver, together with leucin, tyrosin and paralactic acid. The 
urine, moreover, contained biliary pigments, biliary acids, small 
amounts of albumen, and that peptone-like substance which 
often occurs in the urine after phosphorus poisoning in con- 
siderable amount (page 100). The urea was either wholly want- 
ing or was reduced to a minimum. Leucin and tyrosin were 
never absent, so that these bodies may be regarded as almost 
as pathognomonic of acute atrophy of the liver, as albumen is 
of nephritis and sugar of diabetes mellitus. 

* Loc. cit. 

f Ueber acut. Pliosi^liorvergiftung una Leberatrophie, Berlin, 1869, p. 69. 



154 ANALYSIS OF THE URINE. 

B. Detection and Properties. The urine was freed from its tyro- 
sin and leucin by evaporation, the mother liquor was precipi- 
tated with absolute alcohol, the alcoholic solution evaporated, 
and the syrupy residue after the addition of dilute sulphuric 
acid completely exhausted with ether. The united ethereal ex- 
tracts on evaporation left a brown, thin, fluid residue, from 
which long, thin colorless needles, together with brown oily 
dro23S, separated. On treating with water the latter dissolved. 
Sugar of lead solution caused only a slight flocculent precipitate 
in the slightly yellow fluid, by which means it was decolorized. 
Basic acetate of lead gave with the clear, watery filtrate an 
abundant flocculent precipitate, which, after standing a short 
time, condensed to a heavy, granular, crystalline powder. The 
compound was suspended in water and decomposed with sul- 
phuretted hydrogen. The filtrate yielded, after evaporation, 
colorless, very flexible silky needles of the new acid. 

In a pure state oxymandel acid melts at 162'' C. ; it contains 
water of crystallization which escapes when exposed to the air 
at 130^. It is quite soluble in warm water, less so in cold water, 
and readily soluble in alcohol and ether. On heating in a glass 
tube with calcic hydrate brown oily drops appeared which had 
the odor of phenol, and in an aqueous solution gave a dark 
violet color with ferric chloride. 

The simultaneous occurrence of tyrosin and of oxymandel acid 
in the urine, from the chemical relationship of the two sub- 
stances, allows us to suppose that the latter springs from the 
former. This change may be expressed in the following for- 
mula : 

GoH^NOs + O3 -= GO, + NH3 + G JI,04 
[C,,H„NOo + 0,= C A + NH3 + C.JIsOe]. 

By a similar method O. Schultzen and Kiess* obtained from 
the ethereal extract of urine in acute phosphorus poisoning 
warty groups of delicate, colorless, rhombic leaflets of a new 
aromatic acid. On fusing with potassium it yielded cyanogen, 
and on distillation with lime anilin. It melted constantly at 
184° to 185 "" C. ; the silver salt contained 33 '92 per cent, of silver. 
Unfortunately the material did not suffice for an accurate in- 
vestigation. 

*Loc. cit., p. 37. 



ABNORMAL CONSTITUENTS OF URINE. I55 

§ 39. Bkenzcatechin. 
{Oxyphenic Acid.) 

W. Ebstein and J. Muller^ found a substance in the urine of 
a boy four months old, which corresponded with brenzcatechin 
in all of its properties. The urine, colorless when passed, re- 
tained its original color, but if in contact with air, it became 
first reddish, then gradually darker up to the color of burgundy. 
On the addition of potassic hydrate the urine became brownish, 
but later blackish brown, especially on shaking. 

Detection. Two hundred cc. of the urine in question were 
evaporated on the water bath, and the residue repeatedly 
shaken with absolute alcohol. The residue did not become 
brown as mentioned above; the substance in question had, 
therefore, been removed by the alcohol completely. The alco- 
holic filtrate was once more evaporated on the water bath, and 
the residue repeatedly shaken with ether. After evaporating 
the ether there remainded a yellow syrupy mass, which was 
treated with small amounts of water in the cold to separate the 
hippuric acid. This solution gave all of the reactions of brenz- 
catechin. 

1. Evaporated over sulphuric acid on an object glass, white, 
rectangular, prismatic crystals separated. 

2. Alkalies produced a green color in the solution. This 
became gradually greenish brown, brown, and at last almost 
black. 

3. Silver, gold, and platinum solutions were reduced even in 
the cold. 

4. An alkaline solution of copper was reduced on heating. 

5. A solution of ferric chloride immediately produced a color 
which was first dark green, then black. If, further, tartaric acid 
was added to a fluid which contained only traces of ferric chlo- 
ride, the mixture rendered ammoniacal, and then treated with 
some of the aqueous solution of the body in question, the char- 
acteristic violet color was produced, which changed on the ad- 
dition of acetic acid to a faint green, becoming violet again after 
the addition of ammonia. 

'•'" Vircliow's Arcliiv, Band 62, p. 554. 



156 ANALYSIS OF THE URINE. 

6. Acetate of lead gave a white precipitate soluble in acetic 
acid. 

Altliougli, on account of dearth of material, the sublimation 
test and the elementary analysis could not be performed, yet 
the reactions given correspond so completely with those of 
brenzcatechin, that scarcely any doubt exists as to the presence 
of this remarkable substance in the urine in question. Xn 
many respects also the urine corresponded with that in which 
Bcklecker found alkapton (p. 114), which was possibly brenzca- 
techin also. 

Finally it must be mentioned that V. Gorup-Besanez found 
brenzcatechin in the leaves of the wild vine (Amjjelopsis Jwde- 
racea), and Hopj^e-Seyler recognized it as a product of the de- 
composition of starch, cane sugar, sugar of milk, and cellulose, 
after heating these substances from four to six hours with 
water in sealed tubes to from 200^ to 280° C. 



§ 40. Urorubroh^matin and Urofuscoh^matin. 

These two well-characterized pathological coloring matters, 
which appear to stand in close connection to h?ematin, were 
found by F. Baumstark ^ in the urine of a patient suffering with 
leprosy. The color of the urine was at first a deep dark red? 
like Bordeaux wine, and gradually became brown red and toward 
death a pure dark broAvn, almost black. 

Preparation. The urine was subjected to dialysis, when a 
yellow-colored fluid like normal urine passed through the 
membrane with the salts, while a brown slimy substance re- 
mained behind. This readily dissolved in sodic hydrate from 
which the addition of an acid precipitated the urofuscohsema- 
tin, w^hile a beautiful magenta-red coloring matter, urorubrohae- 
matin, remained in solution. The latter separated when the 
red solution was subjected to dialysis. The quantity of the 
two pigments amounted in twelve days to about two grams. 

Urorubrohasmatin (GesHg^NgFesOo,,) was obtained as a bluish- 
black light mass, which is insoluble in water, alcohol, ether, 
and chloroform ; but is soluble in the fixed alkalies, their car- 
bonates and phosphates, and also in alcohol containing acid. 

* Berliner Berichte, Band 7, p. 1170. Pfltiger's Arcliiv, Band 9, p. 568. 



ABNORMAL CONSTITUENTS OF URINE. I57 

None of these solutions are dicliroic, even after the addition of 
a zinc salt. 

The acid solution shows a narrow absorption band in front 
of D and a broad one behind D, so that it appears as if the 
oxyhaemogiobin spectrum were displaced toward the left, yet 
the bands stand nearer each other than in the oxyhoemoglobin 
spectrum. On dilution the narrow band disappears first. The 
alkaline solution shows a band on the right of D, one at E, a 
broad one right of F, and one to the right of G, without the 
blue being absorbed between the two last ; all four bands di- 
minish uniformly on dilution. 

Urofuscohcematin (OesHueNgO.e) is a black, pitchy, shining 
mass with a similar behavior with solvents as the red coloring 
matter. The solutions are not dichroic. In the spectrum a 
shadow appears between D and E, and a second one in front of 
E, which can only be recognized with difficulty. 

In both coloring matters the proportion of carbon to nitrogen 
is as 8 to 68, as in haematin ; both yield on dry distillation 
a distillate, which like the hsematin derivatives investigated 
by Hoppe-Seyler show the pyrrol reactions very beautifully. 
Hsemin crystals cannot be produced from the coloring matters. 

§ 41. Acetone, Alcohol, and Ethyldiacetic Acid. 

F. Kupstein ''^* found acetone and alcohol in the urine of a 
woman forty years old suffering from severe diabetes. The 
breath of this woman had an odor of chloroform, which was 
not noticed in the freshly passed urine, but which became very 
striking after a few hours. 

Detection. During six weeks the urine which was passed was 
daily subjected to distillation, and the distillate after the addi- 
tion of sulphuric acid was repeatedly subjected to fractional 
distillation. The product obtained on the fourth distillation 
had a repugnant urinous odor only slightly resembling that of 
acetone, but it was inflammable, did not mix with sodic hydrate, 
by which it was blackened just as by sulphuric acid, and gave 
a crystalline precipitate with a drop of a concentrated solution 
of acid sodium sulphite (characteristic reaction for aldehyd 
and acetone). The first fraction of this fluid distilled at 67" 

'• Centralblatt f. d, med. Wissenscliaft., 1874, Nr. 55. 



158 AJ^ALYSIS OF TUB URINE . 

C. The distillate was treated with fused chloride of calcium, 
then distilled on the water bath, and the distillate once more 
subjected to similar treatment. That which now volatilized at 
60^ C. (40 cc), which had an odor of acetone, was once more 
distilled in small portions over the water bath, and the portion 
which passed over at 58° C. was employed for the elementary 
analysis. 

Further heating of the chloride of calcium residue over a 
free flame yielded a fluid consisting essentially of ethyl alcohol. 
The alcohol was converted into acetic ether, and this after re- 
peated rectification submitted to analysis. 

Derivation of Acetone and Alcohol. Gerhardt first laid stress on 
the fact that a diabetic urine in which acetone is contained or 
is formed is at the same time characterized by a remarkable 
reaction, namely, treated with ferric chloride, a deep red-brown 
color is produced. This reaction corresponds with the de- 
meanor of ethyldiacetic acid discovered by Geuther, which 
decomposes with great readiness into acetone, alcohol, and car- 
bonic acid. 

Since now the freshly passed urine gave the above reaction 
with ferric chloride, but did not have the odor of acetone, and 
since the iron reaction disappeared on boiling as well as after 
long standing, and instead of it the acetone odor appeared, 
Hupstein supposes that this diabetic urine originally contained 
ethyldiacetic acid, and that by its decomposition acetone and 
alcohol were formed. This supposition gains probability from 
the fact that normal urine treated with ethyldiacetic acid be- 
haves exactly like the above specimen of diabetic urine. Fi- 
nally Kupstein succeeded in isolating a body from a large amount 
of this diabetic urine after acidulating it with acetic acid and 
shaking with ether, which after the addition of an ethereal 
solution of ferric chloride immediately showed a deep brown 
color. 

Since now alcohol could be detected at the same time in the 
urine, Eupstein considers that the presence of ethyldiacetic 
acid in diabetic urine is proved, and by its decomposition ac- 
cording to the formula 

€eH9Na03 + 2H2a=€3Hea + ^^H^O + NaH€03 
(Ethyldiacetic (Acetone) (Alcohol) (Bicarbo- 

acid) nate of sodium), 



URmART SEDIMENTS. 159 

acetone and alcohol are first formed with tlie separation of car- 
bonic acid. 



lY. URINARY SEDIMENTS. 

§42. 

The various deposits which occur more or less in every urine, 
and which are in part passed with it and in part are first sepa- 
rated after a shorter or longer time, are termed urinary sedi- 
ments. The microscope shows that they consist of organized 
and non-organized forms, and that the latter are sometimes 
amorphous and sometimes occur in well-formed crystals. We 
divide sediments, therefore, into organized and non-organized, 
and must distinguish the normal which occur in every urine 
from the pathological sediments. If we leave normal, freshly 
passed urine a short time at rest in a closed glass, light clouds 
of mucus are soon observed to sink, which mucus comes from the 
mucous membrane lining the urinary passages and the blad- 
der, and in which the microscope shows, besides the different 
forms of epithelium from the urinary passages, etc., isolated 
mucous corpuscles. Very frequently, often on very slight dis- 
turbance of the health, the urine soon after cooling deposits 
a sediment consisting of fine or coarse molecules, which are 
easily dissolved again by the application of gentle heat. These 
consist of a mixture of acid urates, in which, according to the 
investigations of Bence Jones, urate of potassium, sodium, and 
ammonium, in feeble combination with an excess " of uric acid 
are never wanting, but with which urate of calcium and mag- 
nesium may also be admixed. (Plate II., fig. 1.) In perfectly 
normal urine so small an amount of urates occurs that they 
remain in solution a long time after cooling ; if, however, the 
urine is very concentrated, or if an abnormal amount of urates 
is separated by the kidneys, they are deposited as a sediment 
very soon after cooling. In most febrile conditions, and under 
all circumstances in which oxidation in the blood is impeded, 
the urates appear most frequently as the long-familiar " sedi- 
mentum lateritium." "We mentioned above, in § 1, that urine 
on standing very frequently underwent an acid fermentation, 
which after a shorter or longer time was always followed by 



160 AWALYSIS OF THE URINE, 

an alkaline one. The urine in tlie first stage of this decom- 
position frequently assumes a somewhat darker color, which 
commences on the surface and gradually and slowly proceeds 
downward. According to the investigations of Pasteur oxygen 
is absorbed during this stage, so that this first act of the de- 
composition of urine must be designated as a process of oxida- 
tion. In the alkaline fermentation, on the contrary, the color 
of the urine becomes gradually paler. 

This act of fermentation stands in the nearest relation to the 
formation and separation of many sediments. If we examine 
the sediment of urates just spoken of under the microscope, 
after the acid fermentation of the urine has commenced, we 
shall find first isolated fermentation spores and in addition 
mucous coagula in broad or narrow curved bands. (Plate II., 
fig. 2.) On increasing acidification the appearance becomes 
changed. The stronger acids are formed, among which may be 
especially mentioned acetic acid, which is never wanting in old 
urine, and decompose the urates ; the latter decrease, but in 
their jDlace beautiful rhombic crystals of uric acid appear, which 
are usually colored yellow, and which are not rarely accom- 
panied by single crystals of calcic oxalate. (Plate II., fig. 4.) 
The separation of uric acid, however, is not always preceded by 
a sediment of urates, but very frequently takes place immedi- 
ately during the stage of acid fermentation in crystals recogniz- 
able by the naked eye as a granular sand w^th a golden lustre. 

According to the investigations of Yoit and Hofman"^ sedi- 
ments of uric acid may separate without previous fermentation, 
since the acid phosphate of sodium decomposes the alkaline 
urates dissolved in the urine with the formation of a basic salt. 
In fact, if equivalent amounts of the solutions of the two salts 
are brought together, after a time crystalline uric acid pre- 
cipitates and the fluid has an alkaline reaction. These facts, 
according to Voit, completely explain the origin of uric acid 
sediments. The action of the acid phosphate of sodium on 
the alkaline urates commences immediately after the forma- 
tion of acid urine ; the urates and then the uric acid are pre- 
cipitated more rapidly when the urine contains a large amount 
of acid phosphate. It is self-evident that this precipitation 

* Zeitschrift f . analyt. Chemie, Band 7, p. 307. 



UBINABT SEDIMENTS. 161 

may take place even witliin the urinary passages and bladder, 
and may tlms give rise to the formation of gravel or calculi. 
This change of the two salts is made more rapid either by a 
more abundant secretion of acid phosphate of sodium or by a 
greater concentration of the urine. When the action of the 
acid phosphate of sodium is rapid, the ]Drecipitate is amorphous, 
and when slow the uric acid separates in the crystalline form. 
Through this transposition the acid reaction of the urine is 
gradually diminished, so that an alkaline reaction may easily 
occur even before the decomposition of the urea, if only just 
enough acid phosphate of sodium is present to form a basic 
salt with the sodium in combination with uric acid. 

After a shorter or longer time, often only after some weeks, 
the second act of the decomposition of urine, alkaline fermenta- 
tion, commences. The urea is then decomposed into carbonate 
of ammonium, according to Tieghem, by the action of a small 
torula, which consists of a chain or heap of small spheres with- 
out an integument, of about 0*0015 millimeter in diameter, and 
without nuclei. This vegetable ferment appears to increase by 
budding, and never develops on the surface of the fluid, but 
either in its interior or at the bottom of the vessel, where it 
finally forms a white deposit mixed with the separated salts. 
As soon as this torula occurs in the urine the decomposition of 
the urea commences. If infusoria appear at the same time, as 
is usual, the urea is decomposed more slowly, but if other 
vegetable productions appear on the surface, by which the de- 
velopment of the torula is hindered, the urine may remain acid 
for months, according to Tieghem.^ If the alkaline fermenta- 
tion has commenced, and if the urine has still only a feebly 
acid or neutral reaction, the sediment has another appearance. 
The crystals of uric acid gradually dissolve and their rudiments 
are frequently beset with prismatic crystals of urate of sodium, 
and here and there with dark spheres of urate of ammonium. 
When the reaction finally becomes alkaline, uric acid has dis- 
appeared, shining crystals of ammonio-magnesian phosphate, 
and dark, often prickly spheres of urate of ammonium, appear 
in the sediment, besides a very large amount of amorphous 

* Concerning the decomposition of urine see also Hallier, '* Gahrungserscliein- 
ungen, etc., etc.," Leipzig, bei W. Engelmann, 1867, and § 52, *' Spores and 
Infusoria." 

11 



162 ANALYSIS OF THE URmE. 

phosphate of calcium, while the surface of the urine is often 
thickly covered with mould. (Plate II., fig. 5.) 

Under pathological conditions both stages of urinary fermen- 
tation may occur in the bladder. ^If the acid fermentation 
occurs, uric acid will be separated and will be passed with the 
urine in the form of coarse or fine gravel. In the alkaline 
fermentation the sediments mentioned are frequently mingled 
with large amounts of pus. (Plate II., fig. 3.) We must not 
leave the fact unmentioned here, that by the use of foul cathe- 
ters, elastic as well as silver, germs of spores, etc., have been 
introduced into the bladder, and thus given rise to the alkaline 
fermentation within the bladder with all of its evil consequences. 
(Niemeyer and Teuffel, Traube and Fisher.) 

Frequently under pathological conditions large amounts of 
calcic oxalate occur in the sediment ; on the other hand, sedi- 
ments of cystin, tyrosin, xanthin, sulphate of calcium,"^ and 
crystallized phosphate of calcium are rare. Of the organized 
substances, in addition to the different forms of epithelium, 
blood and pus corpuscles, renal casts, spermatozoa, and sarcinge 
are frequent found pathologically, and under certain circum- 
stances, masses of cancer and tubercle. We will now consider 
the individual constituents. 



1. Non-Organized Sediments. 
§ 43. Uric Acid. 

Uric acid occurs as a sediment only in strongly acid urine, 
and is frequently accompanied by one of the urates. As a 
sediment it is never colorless, though at times it is pale yelloAv, 
but is usually of a deep-yellow, orange-red, or brown color. Its 
crystalline character is readily recognized even with the un- 
aided eye, and if we examine it under the microscope, it ap- 
pears in the forms mentioned above under uric acid, § 6. 
Four-sided tables or six-sided jorisms of rhombic shape, from 
which often by the rounding of the obtuse angle spindle or 
barrel-shaped crystals are formed, are characteristic. If, how- 
ever, there is any doubt about any crystal, it is only necessary 

* Valentiner, med. Centralblatt, 1863, p. 913. 



URmARY SEDIMENTS. 163 

to dissolve the sediment on an object glass in a drop of potassic 
hydrate, and to add a little hydrochloric acid, when the usual 
forms will soon appear. It is separated from the urates mixed 
with it by heating and filtering; the urates are in solution, 
while free uric acid will remain behind on the filter. Finally it 
can be tested chemically, especially by the murexid test, for 
which very minute quantities of uric acid will suffice. (Plate I., 
figs. 2 and 3 ; Plate II., fig. 4; Plate HI., fig. 1.) 

§ 44. Urates. 

If urates are present in the sediment together with free uric 
acid, they may be separated by heating, as has been indicated, 
and after the filtrate has become cool, they separate. The 
color is very variable grayish white, white, rose red, brown red, 
or purple red ; they often look very much like organized bodies, 
as blood, pus, etc., and can be distinguished from them only by 
the microscope ; they are, however, readily recognized chemi- 
cally by their behavior with nitric acid and ammonia (formation 
of murexid) as well as by their solubility on heating. 

Sediments of urates occur most frequently in febrile condi- 
tions, and under all circumstances in which the respiration, or 
rather oxidation in the blood, is interfered with. 

Bence Jones has examined the sediments consisting of urates 
very carefully, and has found that they contain in 100 parts 
91*06 to 94'36 per cent, of uric acid, 3*15 to 5 per cent, of potas- 
sium, 1*11 to 1'87 per cent, of sodium, and 1*36 to 3*36 per cent, 
of ammonium. If these precipitates are washed with water on 
the filter, they frequently show crystals of uric acid under the 
microscope, and on boiling with water they leave uric acid be- 
hind undissolved. From these experiments it is evident that 
the sediment of amorphous urates often contains far more uric 
acid than is requisite to form acid salts, and that this excess is 
held in such feeble combination by the acid salts that cold 
water sets free crystals of uric acid. Bence Jones succeeded 
in producing artificially a urate of potassium of similar be- 
havior, which was found, on analysis, to be a fourfold acid salt. 
It follows from this that the sediment of amorphous urates has 
no constant composition. It is a mixture of different acid 
urates, which are modified in their crystalline form by other 



164 AJ^ALTSIS OF THE UBINE. 

substances in tlie urine. Tlie potassium salt was found for the 
most part in greater amount than the urate of ammonium or 
sodium ; there is also usually an excess of uric acid in combina- 
tion with these acid salts, so that by washing with water readily 
decomposable quadruple urates are formed, by which the sedi- 
ment is made more susceptible of variation in its composition. 

1. Acid Urate of Sodium in most cases appears in the form of 
amorphous, irregular granules of very small size. Produced 
artificially by dissolving uric acid in a warm solution of ordinary 
phosphate of sodium, it is obtained in microscopic prismatic 
crystals which ordinarily unite to form masses grouped in a stel- 
late form. It is found at times in the urine in a similar form after 
acid fermentation is complete and when alkaline fermentation 
is just commencing. Microscopic examination of the sediment 
in this transition stage often shows very complicated forms. 
The crystals of uric acid separated during acid fermentation and 
now more or less dissolved are covered with beautiful groups 
of prismatic crystals of urate of sodium, while at the same 
time concentrically striped spheres are observed which here and 
there adhere to the prismatic crystals and probably consist of 
urate of ammonium. Such a urine still feebly reddens lit- 
mus as fermentation progresses, and when a neutral reaction 
has already resulted, groups of j)rismatic acid urate of sodium 
crystals are sometimes seen, but now accompanied by beautiful 
large crystals of ammonio-magnesian phosphate. 

Acid urate of sodium dissolves in water with difficulty ; one 
part requires 124 parts of boiling water, and 1,150 parts of cold 
water. On the addition of hydrochloric acid crystals of uric 
acid are separated. 

2. Acid Urate of Potassium is also frequently found in the 
sediment of urates, and is similar to the sodium salt in every 
respect. 

3. Acid Urate of Ammonium. This sediment occurs chiefly in 
alkaline urine mixed with the earthy phosphates. Under the 
microscope it appears in spherical, opaque masses, which are 
studded with peculiar, fine, prominent points. If a drop of 
hydrochloric acid is added to it on a glass slide the familiar 
crystals of uric acid very soon appear. It dissolves in hot 
water but separates again on cooling. If it is treated with a 
very little potassic hydrate, ammonia is evolved ; with nitric 



URINARY SEDIMENTS. 165 

acid and ammonia it gives the well-known murexid reaction, 
like pure uric acid or other urates. (Plate IL, fig. 5.) 

4 Acid Urate of Calcium occurs only rarely and in small 
quantity. It forms a white amorphous powder, difficultly solu- 
ble in water, and on ignition leaves a residue of carbonate of 
calcium. 

A specimen of the acid urine, in which the more or less col- 
ored amorphous sediment is suspended, is moderately warmed 
in a test tube. If complete solution takes place only urates 
are present, and the microscope with a two hundred to three 
hundred magnifying power will show the forms represented in 
Plate II. , figs. 1 and 2. If a crystalline residue remains be- 
hind after heating, it may consist of uric acid Avith which a few 
crystals of calcic oxalate are frequently mingled. (Plate II. , 
fig. 4) In order to test more particularly for any bases pres- 
ent, the sediment is filtered off, washed with dilute alcohol, then 
dissolved in hot water, treated with hydrochloric acid, the uric 
acid which separates after twelve hours filtered off, the filtrate 
evaporated to dryness on the water bath, and the residue 
tested for potassium, sodium, calcium, magnesium, and ammo- 
nium, according to the common methods. 

If the urine has an alkaline reaction, the uric acid in the 
sediment is present mostly as urate of ammonium, which can 
be readily recognized under the microscope from its sea-urchin- 
like spheres. (Plate II. , fig. 5.) All the urates, like pure uric 
acid, give the well-known murexid reaction with nitric acid and 
ammonia. (§ 6, D, 8.) 

The distinction of urate of sodium and potassium from the 
urate of ammonium under the microscope is easy, if the washed 
sediment is treated with hydrochloric acid and allowed to evap- 
orate slowly on an object glass. The microscopic examination 
shows now in addition to the crystals of uric acid, cubes of 
chloride of sodium and chloride of potassium when the urates 
of sodium and potassium are present, and the leafy crystals of 
chloride of ammonium when urate of ammonium is present. 

§ 45. Oxalate of Calcium. 

A. Presence. Though oxalic acid is very widely distributed 
throughout the vegetable kingdom, it occurs only in very slight 



166 ANALYSIS OF THE URINE. 

amount in the animal organism, and then always in combina- 
tion with calcium. In the urine calcic oxalate occurs both 
normally and pathologically as a sediment in the form of con- 
spicuous crystals, especially in cases of disturbed respiration, 
emphysema of the lungs, rachitis, after epileptic convulsions, 
and during convalescence from severe diseases, especially ty- 
phoid fever. Calcic oxalate, however, occurs in solution also 
in urine which does not deposit a sediment, and may remain 
in solution a long time, since, besides other constituents of the 
urine, the acid phosphate of sodium especially possesses the 
power of dissolving calcic oxalate. 

Calcic oxalate frequently accompanies the sediments of uric 
acid and urates. (Plate I., fig. 3 ; Plate II., fig. 4) 

Vegetable food, sparkling wines and beers, also the internal 
use of alkaline bicarbonates and salts with the organic acids, 
and of free uric acid and urates, often increase the amount of cal- 
cic oxalate in the urine. 

The statements of Schunk,^^ according to whom the oxalic 
acid of the urine takes its origin from the decomposition of 
the oxalurate of ammonium which is never wanting in normal 
urine, were not verified by me. In progressing decomposition 
of the urine oxalurate of ammonium is not, as Schunk believes, 
decomposed into oxalic acid and urea, but is transformed directly 
into carbonate of ammonium. t 

B. Microscopic Properties. Oxalate of calcium, artificially pre- 
pared by precipitating a calcium salt with oxalate of ammonium, 
etc., appears under the microscope in perfectly amorphous 
masses, in which no trace of crystallization can be perceived. 
If it separates from the urine as a sediment, however, it shows 
very characteristic forms which are readily recognizable. The 
crystals of calcic oxalate appear in the form of small, elegant, 
shining, perfectly transparent, sharp-edged quadrilateral octa- 
hedra, which are highly refractive, and have a great resem- 
blance to envelopes, but with these there are also sometimes 
a few very pointed ones. Beneke describes also peculiar hour- 
glass shaped crystals, and others which appear like quadrila- 
teral prisms with pyramidal ends. (Plate I., ^g. 3.) 



* Proceedings of the Royal Society, vol. 16, p. 140. 
f Zeitsclirift f. analyt. Chemie, Band 7, p. 330. 



UBmABT SEDIMENTS. 167 

"Very beautiful calcic oxalate crystals can be easily separated 
from a urine wliicli does not deposit a sediment, if it is covered 
with a layer of a dilute solution of oxalate of ammonium with- 
out stirring : I have artificially prepared in this manner a large 
number of the most beautiful forms. The behavior of calcic 
oxalate toward acid phosphate of sodium is interesting. If a 
solution of ordinary phosphate of sodium is treated with officinal 
phosphoric acid, until a drop of the mixture is no longer ren- 
dered turbid by a solution of chloride of barium, a proof that 
the fluid still contains only acid phosphate of sodium, dilute 
solutions of chloride of calcium and oxalate of ammonium can 
be added drop by drop without producing any cloudiness and 
separation of calcic oxalate. If then very dilute sodic hydrate 
is carefully added, drop by drop, to this mixture, which even 
after long standing remains perfectly clear, the calcic oxalate 
in solution separates after a time in very beautiful regular crys- 
tals. The acid solution, which is obtained by boiling uric acid 
with phosphate of sodium, can also hold calcic oxalate in solu- 
tion, and after evaporation yields in addition to urate of sodium 
often very beautiful quadrilateral octahedra of calcic oxalate. 

The crystals are insoluble in water and are scarcely affected 
by acetic and oxalic acids, but are readily dissolved by the 
strong mineral acids. 

C. Detection. Since oxalic acid in the urine always occurs 
only in combination with calcium, it can very readily be recog- 
nized in all cases by its characteristic crystalline forms. The 
peculiar envelope form is especially important, since it ren- 
ders confusion with other sediments impossible. The only 
possibility, perhaps, w^ould be in confounding it with chloride 
of sodium, yet aside from the fact that the latter never occurs as 
a sediment, it is also sufficiently distinguishable from calcic 
oxalate by its solubility in water. Moreover, at times larger 
forms of calcic oxalate occur which have some resemblance to 
the crystals of ammonio-magnesian phosphate to be described 
presently, but the solubility of this double salt in acetic acid, in 
which, as we know, calcic oxalate is insoluble, as well as an 
accurate microscopic examination, does not allow of a mistake. 

If, moreover, the urine is very acid, the crystals of calcic ox- 
alate separate more readily if the free acid is nearly saturated 
and the urine is allowed to stand at rest for a time ; for we 



168 AlfALYSIS OF THE TJEINE. 

mentioned above that the crystals were quite soluble in a solu- 
tion of acid phosphate of sodium. For this purpose the urine 
is placed in a small conical glass, and when the sediment has 
collected in the point, the supernatant fluid is poured off and a 
drop containing the sediment is put on a glass slide. 

Calcic oxalate in solution may be detected with absolute 
certainty in the following manner : The urine to be tested (400 
to 600 cc.) is treated with a solution of chloride of calcium, su- 
persaturated with ammonia, and the precipitate which occurs 
dissolved in acetic acid, of which an excess is to be carefully 
avoided. After twenty-four hours the precipitate, in which uric 
acid is rarely absent, is collected on a small filter, washed with 
water, and a few drops of hydrochloric acid poured over it. Any 
calcic oxalate present is dissolved and the uric acid remains be- 
hind on the filter. The filtrate is diluted in a test tube with 
15 cc. of water, and by means of a pipette is very carefully just 
covered with a sufficient amount of very dilute ammonia. The 
fluids gradually mix if left at rest, and after twenty-four hours 
all of the calcic oxalate present will have collected on the bot- 
tom, and under the microscope will appear in the form of the 
most beautiful octahedra. 

I have frequently been able to prove the presence of tolerable 
amounts of calcic oxalate in solution in the urine by using this 
method, when no trace of it was to be discovered in the sedi- 
ment ; but I have also quite frequently tested normal urine for 
calcic oxalate with a negative result, so that I am still doubtful 
whether oxalic acid is to be reckoned among the normal or 
abnormal constituents of human urine. 

§ 46. Eaethy Phosphates. 

These sediments consist of calcic phosphate and ammonio- 
magnesian phosphate. It is very rare that only one of these 
compounds is met with ; in most cases the two occur at the 
same time. On account of their ready solubility in very dilute 
acids, they cannot form in a strongly acid urine, but appear 
always only when the urine is but very feebly acid, neutral, or 
alkaline, so that the alkaline fermentation has already com- 
menced either in the bladder or outside of it. 

1. Ammonio-Magnesian Phosphate, MgNB.iPQ^,6li^Q [2MgO,KH4 



TTBmABY SEDIMENTS. 169 

OjPOs + 12H0]. This sediment is not met witli in normal urine, 
but always appears in very beautiful crystals when the urine 
becomes very feebly acid or alkaline. In some diseases, in 
severe affections of the bladder and spinal cord, often the whole 
sediment consists of these crystals. Lehmann found a shining 
white sediment in a diabetic urine, which consisted only of the 
ammonio-magnesian phosphate without any traces of calcium. 

The crystals of this double compound (triple phosphate) 
are always very easy to recognize from their conspicuous forms. 
The forms which occur most frequently are combinations of the 
rhombic vertical prism, which have a great resemblance to the 
lid of a coffin. (Plate II., fig. 3, ^g. 5.) The crystals are insolu- 
ble in hot water, but acetic acid readily causes them to disap- 
pear, by' which they are distinguished from similar forms of 
calcic oxalate. They are not attacked by alkalies. 

2. Phosphate of Calcium, €3,2 (PO,) [3CaO,PO J and GallPO, [2Ca 
0,HO,PO.]. This is an amorphous, and frequently also a crys- 
talline powder. Phosphate of calcium is insoluble in water 
though soluble in acids, even acetic acid, and is precipitated 
from these solutions in an amorphous form by alkalies. It oc- 
curs also only in feebly acid, neutral, or alkaline urine. 

Frequently, especially in urine with a feebly acid reaction, 
the phosphate of calcium is only held in solution by carbonic 
acid, and immediately separates in white flakes, very like a 
coagulum of albumen, as soon as the carbonic acid is driven 
off by heat. 

Not very rarely also sediments of crystallized phosphate of 
calcium are found which frequently occur alone, but at times 
mixed with triple phosphate. The size, form, and grouping of 
the crystals of phosphate of calcium in the sediment varies very 
considerably, yet they always present sufficiently marked pecu- 
liarities to be immediately recognized under the microscope. 
The crystals are sometimes isolated, sometimes collected to- 
gether; the latter is more frequent, in which case they form 
clumps and rosettes. Sometimes they are thin and needle- 
shaped, and then often form spherical rosettes of crystals by 
crossing each other at right angles and lying together ; at times 
they are narrow and smooth and have sharp-pointed ends. But 
very frequently the crystals are thick, and more or less wedge- 
shaped, and are joined together by their pointed ends, so that 



170 ANALYSIS OF THE URINE. 

tliey describe more or less complete parts of a circle. The 
broad free end is usually somewliat oblique, and the more per- 
fect crystals appear to be formed of six surfaces. Urine which 
separates crystallized phosphate of calcium in large amount is 
usually pale, considerable in quantity, and has a feebly acid 
reaction, but readily becomes alkaline in consequence of an ad- 
mixture of mucus. Bence Jones says that this sediment may 
be produced at pleasure by taking lime-water or acetate of 
calcium. According to him, the crystallized phosphate of cal- 
cium is €aHP04 [2CaO,HO,POJ, while the amorphous is Ga. 
2(P0,) [3CaO,PO,]. 

The two conditions on which the appearance of crystallized 
phosphate of calcium depends, but which need not exist to- 
gether, are an excess of phosphate of calcium and a feebly acid 
reaction of the urine. If, therefore, normal urine is treated 
with a little chloride of calcium and nearly neutralized with 
sodic hydrate, it is often possible to obtain numerous crystals 
perfectly similar to those described. 

Detection. The recognition of the earthy phosphates pre- 
sents no difficulties, especially the first-mentioned, since its 
presence, as well as its microscopic and chemical properties, 
characterize it sufficiently. If they should occur mixed with 
other sediments, the following points will serve as distinguish- 
ing characteristics : Urates dissolve readily on heating the 
urine, phosphates remain undissolved even at a boiling temper- 
ature. Calcic oxalate, which in some forms may well be con- 
founded with the ammonio-magnesian phosphate, is insoluble 
in acetic acid, whereas the latter is readily taken up. Free 
uric acid probably never occurs with the earthy phosphates, 
yet uric acid is readily recognizable both by its crystalline form 
and its solubility in alkalies. The murexid reaction finally 
Avould remove all doubt. 

The familiar reactions serve to detect calcium, magnesium, 
and phosphoric acid. A small portion of the acetic acid solu- 
tion is tested for phosphoric acid with uranium solution. The 
calcium is precipitated from a second specimen by an excess of 
oxalate of ammonium, and the phosphate of magnesium is pre- 
cipitated from the filtrate by ammonia. 



URINARY SEDIMENTS, 171 



Formula : O.H.NSOo 



47. Cystin. 






' Carbon 


29-75 


&o 


Hydrogen 


5-78 


b'o J 

oj - 


Nitrogen 


11-57 


Sulphur 


26-45 




^ Oxygen 


26-45 



100-00 

A. Presence. Cystin was first discovered in a urinary calculus, 
but later it has been found that, besides in sucli concretions, 
cystin often occurs also dissolved in the urine and may be pre- 
cipitated by acetic acid. It also occurs as a sediment mixed 
with urate of sodium. The occurrence of cystin as a calculus 
is rare, for of one hundred and twenty-nine obtained only two 
contained cystin. (Taylor.) Eecently Cloetta found cystin in 
the fluids of the kidney together with inosite and hypoxanthin. 
Scherer discovered it once in the liver recently. J. Dewar and 
A. Gamgee state that they found cystin in the sweat in a few 
cases. 

Julius Miiller "^ describes a calculus containing cystin which 
was removed by operation from the bladder of a boy six and a 
half years old. This boy's urine, obtained before the operation 
only in small amount, was alkaline, and deposited a sediment 
which was free from uric acid and earthy phosj)hates, and 
abounded in mucous corpuscles ; there was only a little urate 
of sodium in solution, but much chloride of sodium. The calcu- 
lus weighed 268 J grains and contained 55-55 per cent, of cystin. 
Directly after the operation the nrine had an acid reaction, a 
mucous sediment, and contained less uric acid and earthy phos- 
phates than normal urine. Eight weeks later, however, the 
alkaline reaction recurred again, and it contained much chlo- 
ride of sodium and urea, but only traces of uric acid. On quiet 
standing it deposited a sediment of ammonio-magnesian phos- 
phate and cystin, which, after removing the magnesium salt 
with acetic acid, was easily recognizable under the microscope 
by its cystalline form. The filtered urine also gave within 

*Arcliivd. Pliarm., Marz, 1853, p. 228. 



172 ANALYSIS OF THE URINE. 

twenty-four hours after the addition of acetic acid a precipitate 
soluble in ammonia, on the evaporation of which most excellent 
microscopic tables of cystin were obtained. Erom this it fol- 
lows that the production of cystin in the organism of the boy 
continued also after the operation. 

Toel ^ made interesting observations upon the formation of 
cystin on two girls in Bremen, by whom this remarkable body 
was constantly passed with the urine, as the result of a kidney 
trouble (nephritis calculosa), partly in solution, and partly as a 
sediment. The amount of cystin secreted amounted on the 
average to 14 grm. in twenty-four hours in each. Another 
very interesting case, in which cystinuria lasted for years, is 
described by Bartels.f 

Not infrequently large concretions of almost chemically pure 
cystin are passed with urines containing cystin as a sediment. 
The little stones of yellow color and crystalline structure vary 
from the size of the head of a pin to that of a pea, and are so 
characteristic even in their exterior that they cannot readily 
be confounded with any other urinary concretion. Whoever 
has once seen them will always recognize them again at the 
first glance. 

B. Microscopic Properties. Cystin crystallizes under the mi- 
croscope in colorless, transparent, six-sided plates or prisms. 
Since, however, uric acid at times crystallizes also in six-sided 
tables, we must not rely on microscopic examination alone, but 
must carefully examine such a sediment chemically also. (Plate 

in., fig. 4.) 

C. Chemical Properties. — 1. Cystin is neutral without odor or 
taste, insoluble in water, yet soluble in mineral acids and oxalic 
acid, with which it forms saline, easily decomposable com- 
pounds. Acetic and tartaric acids do not dissolve it. 

2. If cystin is heated with nitric acid, it dissolves with de- 
composition, and on evaporation leaves a reddish-brown mass 
which does not give the murexid reaction with ammonia. 

3. Cystin does not fuse on being heated on platinum foil, 
but it inflames and burns with a bluish-green flame, while a 
sharp, acid, characteristic odor, like that of hydrocyanic acid, 

*" Annal. d. Cliem. u. Pliarm., Band 96, p. ^4 et seq. 
f Virchow's Archiv, Band 26, p. 419. 



URmABY SEDIMENTS. 173 

is evolved. On dry distillation it yields ammonia and a stink- 
ing oil, leaving a residue of porous charcoal. 

4. Alkaline hydrates and carbonates, as well as ammonia, 
dissolve cystin with ease, but carbonate of ammonium does not. 
It is, therefore, always precipitated from its acid solution by 
carbonate of ammonium, and from its alkaline solution by 
acetic acid. 

5. If cystin is boiled with potassic hydrate in which oxide of 
lead has been previously dissolved, a large amount of lead sul- 
phide separates. (Liebig.) 

6. If cystin is boiled with alkaline hydrates, ammonia and a 
gas which burns with a blue flame are evolved. 

7. If a little cystin with a few drops of sodic hydrate are 
heated to boiling on a silver foil, there results a brown or black 
spot of sulphide of silver which cannot be washed away. 

8. If cystin is dissolved by heating with potassic hydrate, 
diluted and treated with a solution of nitroprussiate of potas- 
sium, the well-known, beautiful, violet sulphur reaction occurs 
with great magnificence. (J. Miiller.) This reaction is particu- 
larly beautiful. 

D. Detection. Cystin is characterized especially by its crys- 
talline form, its solubility in the mineral acids and alkalies, 
and by its behavior with nitric acid and with heat. Liebig has 
given besides for its recognition the reaction with caustic pot- 
ash and lead oxide, which produce when boiled with cystin a 
very abundant precipitate of suljohide of lead. But in employ- 
ing this reaction we must bear in mind that other bodies con- 
taining sulphur, such as albumen, fibrine, etc., exhibit a like 
behavior, so that we must first be convinced of the absence of 
these substances, and remove them if present. 

Cystin is easily separated from the earthy phosphates and 
the urates by boiling and treating with acetic acid, since it is 
soluble neither in boiling water nor in acetic acid, while the 
latter are readily dissolved thereby. Uric acid which, as has 
been mentioned, at times also crystallizes in six-sided tables, is 
sufiiciently characterized by its murexid reaction, since cystin 
treated in the same way leaves only a reddish-brown residue. 



174 ANALYSIS OF THE URINE 



§48. Tyeosin. 

(Compare § 37.) 

Stadeler and Frericlis observed in the urine of a woman suf- 
fering from acute atrophy of the liver, after standing awhile, a 
sediment of greenish-yellow spherical crystals, which consider- 
ably increased after slight evaporation of the urine. It was 
extracted with dilute ammonia, and the first crystals which 
formed from the solution were recognized as tyrosin. Another 
more soluble body, probably homologous with tyrosin, whose 
quantity of nitrogen amounted, not as in tyrosin to 7*73 per 
cent., but to 8*83 per cent., remained in the mother liquor. 

O. Schultzen and L. Eiess * found the same sediment in acute 
atrophy of the liver. The clear urine, removed from the bladder 
with the catheter, on cooling deposited delicate almost colorless 
needles aggregated into sheaf-like bundles, which were recog- 
nized by all of the reactions as tyrosin. 

§ 49. Xanthin (Hypoxanthin ?). 

(Compare § 5. ) 

Bence Jones t found in the urine of a boy nine and a half 

years old, who three years before had had the symptoms of 

renal colic, whetstone-shaped microscopic crystals (fig. 3, a), 

Yic, 3. which, as the figure shows, might at 

/\ fN /p first sight be considered as uric acid, 

OaQ W/l'^ 0^ ^^"^^ ^^ heating the cloudy urine the 

^Oc:>(j W-\ O/OrsQ . sediment quickly dissolved. This sed- 

^^ ^~" ' iment collected on a filter and washed 



0'^^^^^^^(ffpl^(f^ ^^^^^^ alcohol gave the following reac- 



tions: The crystals were soluble in 

O water and hydrochloric acid, solution 

^ ^ took place in nitric acid without effer- 

vescence, and after evaporation a yel- 
low residue remained. The hydrochloric acid solution on 
evaporation separated crystals of the form 6, which were solu- 
ble in water. The sediment also readily dissolved in alkalies. 

* Loc. cit., p. 70. 

f Cliem. Centralblatt, 1868, p. 847. 



URINAR r SEDIMENTS. I75 

The urine always had a tolerably high specific gravity, and at 
times contained traces of albumen, but the sediment, according 
to Bence Jones consisting of xanthin, did not appear again 
later. 

G. Lebon^ describes an interesting calculus containing xan- 
thin. It consisted first of all of a layer of phosphate of calcium 
and ammonio-magnesian phosphate one millimeter thick, then 
followed a second layer of calcic oxalate of equal thickness, 
and finally the chief mass consisting of xanthin and a small 
amount of urate of calcium. This inner stratum formed an 
amorphous cinnamon-brown mass which assumed a waxy lustre 
on being rubbed. The solution in hydrochloric acid on slow 
evaporation left a residue of beautiful hexagonal lamellae of 
chloride of xanthin. 

II. Organized Sediments. 
§ 50. Mucus AND Epithelium. 

It is well known that animal mucus is separated from the 
mucous membranes and contains the epithelial cells in their 
different forms suspended in it. Every urine contains such 
mucus which comes from the urinary passages and bladder, 
and very soon separates Avhen at rest as a light cloud. If such 
urine is filtered, the mucus for the most part remains on the 
filter in isolated transparent colorless clumps, which shrink and 
form a shining varnish-like coating. 

The characteristic constituent of mucus is mucin, a derivative 
of the protein bodies, which when dissolved in a fluid, even in 
small amount, imparts to it a viscid stringy quality. A solution 
of mucin does not coagulate on boiling (distinction from albu- 
men), but it does on the addition of alcohol, by which the mucus 
is precipitated as a fibrinous coagulum. Acetic acid and a solu- 
tion of alum separate mucus in thick flakes ; the stringy mass 
precipitated by acetic acid has a certain resemblance to coagu- 
lated blood fibrine. (Funke, Taf. XL, fig. 6; 2^^ Aufl., Taf. XV., 
fig. 6.) Mineral acids also precipitate a solution of mucin ; 
yet the precipitates which take place are readily soluble in a 
slight excess of the acid. Mucin is chiefly distinguished from 

*Compt. rend., Band 73, p. 47. 



176 ANALYSIS OF THE URINE. 

pyin, wliicli occurs in pus, in that it is not precipitated either 
by a solution of corrosive sublimate or one of sugar of lead, 
though it is by the basic acetate of lead. 

In the mucous sediment of a normal urine there appear un- 
der the microscope, besides the distinctly nucleated, variously 
shaped epithelial cells of the urinary passages, etc., isolated 
mucous corpuscles in the form of round, very granular cells, 
containing one or several nuclei, which do not differ from the 
colorless corpuscles of the blood, lymjDh, chyle, and pus in any 
essential particular. (Plate I., fig. 4, 5, and 6; Plate II., fig. 1, 
2, and 3; Plate III, fig. 3.) 

If the secretion of mucus is increased by disease, the little 
cloud described above as occurring in normal urine is often 
enormously augmented, and shows large amounts of mostly 
well-preserved epithelial flakes and mucous clumps. If the 
mucous sediment which settles on standing is free from pus 
and consists only of mucus, the filtered urine is free from albu- 
men, while if pus is present at the same time the urine always 
contains an amount of albumen corresponding to the pus serum. 
(Compare Pus, § 52, B.) 

In gonorrhoeas the mucous corpuscles coming from the 
urethra differ from uric acid, etc., by their size and their clear, 
slightly granular appearance. In affections of the prostate the 
amylaceous bodies of this gland ajDpear, and frequently, as at 
times after gonorrhoea, long mucous plugs, which under the 
microscope appear to be composed of mucous corpuscles closely 
adherent to each other. 

1. Normal urine always contains only traces of mucin in so- 
lution. An increase, according to Reissner," occurs in various 
acute febrile affections, as pneumonia, pleuritis, typhoid fever, 
intermittent fever, pulmonary and intestinal catarrhs, menin- 
gitis, acute delirium, and epileptic attacks with irritation of 
the vascular system, etc. Often the mucin alone appeared at 
the commencement of the fever, a few days later albumen was 
also found, which disappeared again after a longer or shorter 
time, while the mucin continued a few days longer. Cases in 
which there was a large amount of mucin which lasted a long 
time without albumen were rare. The microscope showed for 
the most part a large number of epithelial cells of very different 

* Arcliiv f. path. Anat., Band 24, p. 191. 



ubiwahy sediments. 177 

sorts ; mucous coagula were often very abundant, but at times 
were only sparingly present. Sometimes mucous and pus cells 
were entirely wanting. Acetic acid is especially valuable for the 
detection of dissolved mucin ; it causes in every urine contain- 
ing mucin a uniform cloudiness insoluble in an excess of the 
acid. Only in rare cases does a flocculent deposit occur after 
long standing, but if the urine before the addition of acetic 
acid was diluted with water to several times its volume, there 
results from the cloudiness, when there is not too small an 
amount of mucin, a tolerably coarse flocculent precipitate which 
settles after some hours' standing, and under the microscope 
appears as a uniform finely granular mass with a few uric acid 
crystals imbedded in it. Tartaric acid acts like acetic acid. 
Mineral acids when very dilute, and added drop by drop to the 
urine, give a precipitate which is soluble in the slightest excess 
of acid. A few drops of hydrochloric acid will also dissolve 
the cloudiness caused by acetic acid immediately and com- 
pletely, when added soon after the latter. 

Many urines in very febrile conditions also give a cloudiness 
with acetic acid insoluble in an excess, but which disappears 
on heating and does not recur again, if the urine is sufficiently 
diluted with water before the addition of the acid. This cloudi- 
ness, which is probably caused by urates, is, therefore, easy to 
distinguish from a precipitation of mucin. 

The dissolved mucus is frequently precipitated in the form 
of mucous coagula at the beginning of acid fermentation, pro- 
bably by the free acids formed. They appear in narrow and 
broad curved bands containing very fine points and granules 
arranged in rows, and very frequently sediments of acid urates 
accompany them. These mucous coagula (Plate II., fig. 2) 
have at times a certain resemblance to granular casts from the 
kidney (Plate I., fig. 6), and may, therefore, give rise to mis- 
takes. With a little experience, however, they are both easily 
distinguished. 

2. Epithelial cells are found in three different forms : 

a. Eound cells from the urinary tubules of the kidney, and from 
the deeper layers of the mucous membrane of the pelvis of the 
kidney. They are for the most part swollen by the salts con- 
tained in the urine, and appear as complete spheres with dis- 
tinctly formed nuclei. 
12 



178 Al^ALYSTS OF THE URINE. 

The epitlielium of the male urethra is very similar to renal 
epithelium, so that the two can scarcely be distinguished by 
the microscope. When renal epithelium is present, the urine 
usually contains albumen at the same time. 

b. Conical and tailed cells in most cases have their origin 
from the pelvis of the kidney. These cells are usually twice as 
long as they are broad, and are broader at one end than at the 
other. The spindle-shaped prolongation occurs either at one 
end or at both. 

c. The flat cells come either from the vagina or bladder. In 
most cases they form irregular polygonal lamellae with distinct 
nuclei situated nearly in the centre. 

§ 51. Blood. 

The occurrence of blood in the urine is not a very rare ap- 
pearance and its recognition presents no special dijB&culties. 
For our purpose the blood corpuscles, and especially their mi- 
croscopic properties, are of special importance. 

A. llicroscojnc Properties. Normal blood corpuscles are small, 
round, solid structures, which seen under the microscope pre- 
sent a shape not to be confounded with any other substance ; 
they appear as thick, circular, slightly biconcave, yellow disks, 
with rounded edges. Their size in human beings amounts to 
about 0-00752 mm. (Plate I, fig. 6; Plate III., fig. 1 and 2.) 
The normal forms, however, suffer peculiar modifications and 
changes due to the presence of many alkaline salts and other 
substances. These changes are of special importance for our 
purpose. 

1. Action of Water on Blood Corpuscles. According to the 
amount of water added and the time during which it acts, the 
blood corpuscles undergo various changes, which are figured 
in Plate III., fig. 2, proceeding from left to right. The first 
result of the action of w^ater is, that the single cells swell up, 
at the same time assume a more lenticular shape, and finally 
become spherical; this takes place because their central de- 
pression disappears and gradually arches out, which necessa- 
rily causes a diminution of the diameter of the disks. The 
corpuscles now appear smaller, the central shadow disappears 
gradually, and in its place a circular one appears on the edge. 



UPJNARY SEDIMENTS. 179 

If tlie action of tlie water lasts for a long time, the cells be- 
come constantly fainter and paler, and finally appear only as 
hyaline bladders, which soon become entirely imperceptible 
and disappear. 

2. Action of Saline Solutions on Blood Corpuscles. If normal 
blood corpuscles are covered with a concentrated solution of a 
neutral salt, for example sodic sulphate, they undergo quite 
rapidly a strong contraction, which under the microscope is 
chiefly indicated by an increase of the central depression; 
the shadow which indicates this reaches nearer to the edge 
of the disk than in normal blood corpuscles. The edges are 
usually no longer circular, but are mostly more or less dis- 
torted, oblong, angular, and also not smooth, but notched or 
toothed. If, further, blood corpuscles, which have become in- 
visible by the action of water, are treated with a concentrated 
solution of sulphate of sodium, they become visible again, but 
now appear in the distorted, angular, and toothed forms just 
described. (Plate III., fig. 2, lower right side.) 

3. Caustic alkalies, as well as several organic acids, as, for 
example, acetic acid, cause the blood corpuscles to become 
very much swollen and distorted, and destroy them more or 
less rapidly. 

The important constituent of the red blood corpuscles is the 
haemoglobin (blood-coloring matter, hsematocrystallin), which 
may be obtained more or less easily in a crystalline form. 
(Funke, Taf. X., fig. 1-6 ; 2^" Aufl., Taf. IX. u. X.) The beautiful 
blood-red solution shows on great dilution (joVo)? when it is 
examined by the spectroscope in a layer of fluid one ctm. thick^ 
two absorption bands between the Frauenhofer lines D and E 
in the yellow and green of the spectrum. (Plate IV.) The 
band situated nearer D is more sharply defined, and also dis- 
appears later than the other on dilution. If, however, such a 
solution of oxyhsemoglobin is allowed to remain in a closed 
vessel for a time, or if the oxygen is removed from it by a few 
drops of sulphide of ammonium, the arterial color gradually 
disappears. In the spectrum the two absorption bands are 
now absent, and instead, about in the middle between the 
spectral lines D and E, there is a broad, poorly defined band. 
On shaking with air this disappears, and the absortion bands 
characteristic of oxyhsemoglobin appear again. If a solution of 



180 AliALYSIS OF THE URINE. 

lisemoglobin is heated a few minutes to 70° or 80^ C, it de- 
composes into ligematin and coagulated albumen with change of 
color. Basic acetate of lead does not precij^itate a solution of 
pure haemoglobin. After standing a long time, especially at 
blood heat, a darker color and acid reaction occur, the hae- 
moglobin becomes converted into methsemoglobin, which is an 
intermediate product formed during the change of haemoglo- 
bin into haematin and albuminoid matter, and which is found 
in old extravasations of blood and also in the urine after de- 
struction of the blood corpuscles. Examined with the spectro- 
scope an acid solution of methaemoglobin sulB&ciently dilute 
shows almost the same spectrum as an acid solution of pure 
haematin. Both give only one absorption band between the 
lines C and D, which lies rather nearer C. (Plate IV.) If the 
solution is rendered alkaline the bands draw nearer to D, and 
become feebler and less sharply defined. Basic acetate of lead 
precipitates a solution of methaemoglobin. We are indebted 
to Hoppe-Seyler and Stokes for these excellent reactions. 
B. Detection. 

1. The Urine contains Blood Corpuscles. If the urine is acid, 
the blood corpuscles remain unimpaired a tolerably long time, 
or at most become somev\^hat crenated, but they are usually 
swollen and approach the spherical form. Their color is paler 
than in the normal condition, but they are always at the same 
time sharply defined, and are no longer arranged in rows. All 
of these changes indeed are to be attributed to the water and 
salts contained in the urine according to the modifications de- 
scribed above. (Plate I., fig. 6 ; Plate III., fig. 1 and 2.) When 
the amount of blood is small, the urine is allowed to stand 
quietly in a conical glass for a long time. The blood cor- 
puscles then settle to the bottom as a beautiful red sediment, 
and may generally be recognized as blood with the unaided 
eye. The clear filtered urine, Avhen blood is present, always 
contains a corresponding amount of albumen also, which may 
be recognized according to § 23, D. 

If such a urine sufficiently diluted is examined with the spec- 
troscope, it shows the absortion bands between the lines D and 
E, which were described above as characteristic of haemoglo- 
bin. (Manipulation : see below, 2, a.) (Plate lY.) 

2. The Blood Corpuscles are destroyed; the Urine contains 3Ie- 



URINARY SEDIMENTS. 



181 



thcGmoglobin. Tlie urine may be colored reddish brown, or even 
black, by methaemoglobin. It is tested ^s follows : 

a. Some of tlie clear filtered urine is poured into a vessel, 
«, fig. 4, of plate glass, with two parallel walls ; this is placed 
close to the slit of the spectroscope, lighted with sunlight or a 
bright gas or oil lamp, and the spectrum observed through the 
telescope, h. If the amount of methaemoglobin is not too great, 
and the urine consequently not too strongly tinged, the char- 
acteristic bands between the lines C and D will appear imme- 

FiG. 4. 




diately somewhat nearer C than D. (Plate lY.) On the other 
hand, when there is very considerable methsemogiobin, a greater 
or less part of the whole spectrum will be absorbed and will 
only become clear on diluting the urine under examination with 
water, until the absorption bands characteristic of methaemo- 
globin are seen. 

b. A second specimen of the filtered urine is heated to boil- 
ing. If methaemoglobin is present, a brownish-red coagulum 
is formed, which consists of haematin and an albuminoid body : 
after drying the color becomes almost black. If we treat such 



182 ANALYSIS OF THE UBINE. 

a coagulum, previously washed, with alcohol containing sul- 
phuric acid, and heat gently, it will assume a more or less red 
or reddish-brown color, and after sufficient concentration will 
show in the spectrum the absorption bands described under a, 
as characteristic of haematin and methsemoglobin. (Plate IV.) 

c. A third specimen of the urine under examination is treated 
with a little sodic hydrate, heated to boiling and allowed to 
stand for a time. The earthy phosphates which separate carry 
down the hsematin formed by the decomposition of the hae- 
moglobin or methaemoglobin, and appear sometimes as a 
brownish-red and sometimes as a beautiful blood-red precipi- 
tate, which is often dichroitic, playing into green by reflected 
light. This reaction does not allow of a discrimination be- 
tween haemoglobin, methaemoglobin, and haematin. 

If the phosphate precipitate is colored by rhubarb, senna, or 
santonin, and not by haematin, it is recognized by the fact that 
it does not, like the haematin precipitate, become dichroitic by 
the action of potassic hydrate, but in time becomes violet, es- 
pecially when exposed to the air. 

d. Tannin is a very valuable reagent for precipitating small 
traces of blood. The fluid in question is treated with a little 
ammonic or sodic hydrate, then with a solution of tannin, and 
lastly with acetic acid until it has a distinctly acid reaction. 
If blood is j)resent a distinctly colored precipitate forms, which 
quickly settles to the bottom of the fluid. This precipitate is 
tannate of haematin. After washing and drying, it is specially 
fitted for the production of haemin crystals. For this purpose 
a portion of the dry precipitate is placed on a glass slide, a trace 
of chloride of sodium is added, and then glacial acetic acid. So- 
lution takes place at a gentle heat, and after cooling, the well- 
known characteristic haemin crystals will be found under the 
microscope in large numbers. (Struve.)^ The reaction is ex- 
tremely delicate. By performing it in the manner described, 
Bergt succeeded in proving by the most beautiful haemin 
crystals, the presence of a drop of blood in 450 cc. of urine. 

e. Another method for detecting blood in the urine has been 
given by Almen.J A few cc. of tincture of guiacum are mixed 

* Zeitschrlft f. analyt. Chemie, Band 11, p. 29. 

f Hyiea, Band 34, 2, Stockholm, 1873. 

i Zeitsclirif t f. analyt. Cliem., Band 13, p. 104. 



UBINARY SEDIMENTS. 183 

with an equal volume of oil of turpentine, it is sliaken till an 
emulsion is formed, and tlien the urine to be tested is carefully 
added. When the emulsion comes in contact with the urine, 
the guiac resin is quickly precipitated as a white, later dirty 
yellow or green precipitate. If the urine contains blood, even 
traces merely, the resin is colored more or less intensely blue, 
often almost indigo blue. In normal urine or in urine con- 
taining albumen from pus, this blue coloration does not occur. 



§ 52. Pus. 

When urine contains pus it can only be detected with cer- 
tainty by the microscope. 

A. Blicroscopic Properties. Normal pus corpuscles appear 
under the microscope as round, pale, faintly granular bodies of 
variable size. It is of especial importance that a distinct nu- 
cleus may usually be perceived in them, which in many cor- 
puscles is single, but in others appears divided and multiple. 
(Plate I., fig. 6 ; Plate III., fig. 3.) All pus corpuscles do not 
have a sharp contour, but in many cases only a faint and indis- 
tinct one. 

1. Action of Water on Pus Corpuscles. If fresh pus is consider- 
ably diluted with distilled water, the corpuscles are seen to 
swell up very much, and become extremely pale and delicately 
bordered ; at the same time their granular surface usually dis- 
appears, whereas the nuclei become more distinct and small 
dark punctiform granules are seen. (Funke, Taf. XL, fig. 4; 
'r Aufl., Taf. Xy., fig. 4) 

2. Action of Acetic Acid on Pus Corpuscles. If dilute acetic or 
any other organic acid, or even very dilute mineral acids are 
allowed to act on pus, the corpuscles swell up, so that some- 
times they assume double their usual size ; their surface then 
loses its granular appearance, the coverings become very hya- 
line, and not unfrequently burst, so that here and there, with a 
good light, their jagged and broken remnants may be distin- 
guished. The nuclei already mentioned become very distinct, 
of different shapes and numbers, appearing partly as simple, 
round, oblong, spindle and horseshoe-shaped bodies, and partly 
as double, triple, and quadruple ones, variously grouped accord- 



184 ANALYSIS OF THE UEmE. 

ing as they are formed by division of tlie single nucleus. (Plate 
III., fig. 3, upper half.) 

3. Caustic Alkalies quickly destroy pus corpuscles, but com- 
plete solution does not take place. The corpuscles frequently 
remain visible for a short time, but disappear after the addition 
of water, and leave only a gelatinous residue in which isolated 
bright or dark points may be recognized. 

B. Detection. Pus settles very quickly in acid urine when at 
rest, and when the supernatant urine has been drawn off with a 
siphon, it may be easily subjected to microscopic examination. 
(Plate L, fig. 6 ; Plate II., fig. 3 ; Plate III., fig. 3.) Purulent 
sediments are not very rarely accompanied by blood corpuscles, 
which may be recognized by their reddish color, but more surely 
by the microscope. In both cases the clear filtered urine con- 
tains corresponding amounts of albumen. (§ 23, C.) Pus suffers 
an essential change in alkaline urine, which is the more impor- 
tant, since frequently in catarrh of the bladder, etc., alkaline 
urine is passed with considerable amounts of pus. Alkalies 
change pus into a gelatinous mucous mass, which adheres 
tenaciously to the wall of the vessel, and under the micro- 
scope pus corpuscles no longer appear, so that it may readily 
be mistaken for mucus. But in most cases it is possible to find 
in addition to this viscid gelatinous mass a tolerable number 
of pus cells suspended in the urine if it is examined under 
the microscope as soon as possible after being passed. The 
behavior of pus with alkalies just cited may serve for distin- 
guishing it from mucus. The sediment under examination, 
obtained by settling, is treated with concentrated potassic hy- 
drate ; pus is coagulated by it into the gelatinous mass spoken 
of, while mucus dissolves to a thin fluid with flakes. (Donne's 
pus test.) 

Since, as observed above, when pus is present, the urine 
always contains albumen also from the pus serum, an ap- 
proximate estimation of the quantity of pus may be made from 
the amount of the albumen in the urine previously filtered, 
provided there is sufiicient ground for excluding a simultaneous 
real albuminuria. Moreover, when blood is present at the 
same time, this is also to be taken into account as the source of 
a part of the albumen. 



URINARY SEDIMENTS. 185 



§ 53. Casts. 

In many diseases, but especially in Briglit's disease of the 
kidneys, peculiar tubular or cylindrical bodies, wliicli liave for 
a long time been the subject of investigation, are observed in 
the sediment of the urine. They vary in texture more or less, 
for which reason Lehmann distinguishes three different kinds : 

1. Tubes which appear to consist of the epithelial lining of 
the tubules of Bellini ; these appear in almost every inflamma- 
tory irritation of the kidneys, and form regular tubes in which 
the small cells and cell nuclei appear to be grouped almost like 
a honeycomb. (Plate I., fig. 4) 

2. Cylinders which appear to consist of fresh exudation, which 
was formed in the tubes of Bellini and has retained their form. 
These cylinders form granular masses which are frequently 
covered with blood and pus corpuscles. They aj)pear to con- 
sist of fibrine, at least their ready solubility in alkalies indicates 
this, while the blood and pus corpuscles attached are partly 
destroyed and partly remain suspended in the fluid. They are 
always found in Briglit's disease.^ (Plate I., fig. 6.) 

3. Finally, casts are sometimes observed, which consist of 
hollow cylinders with hyaline walls, and can be distinguished 
from the surrounding fluid under the microscope only with 
care. Frequently they lie together, form folds and appear as 
if twisted on their axis. They usually occur only isolated in 
the chronic form of Bright's disease. (Lehmann.) (Plate I., 
fig. 5.) 

Detection. For the certain detection of these very important 
structures, the urine, which in most cases contains considerable 
albumen, is allowed to stand several hours in a conical glass. 
The collected sediment, mostly white and flaky, or, when other 
matters are present also, forming thick masses, is first exam- 
ined with a power of one hundred and eighty or two hun- 
dred diameters, and if these structures are present they can 
readily be seen. At most the very hyaline cylinders mentioned 
under 3 may remain unobserved, but immediately become ap- 
parent when the object is colored yellow by the addition of a 
solution of iodine in iodide of potassium, or red by the addition 

* Frericlis, BrigM's disease. 



180 AJ^ALYSIS OF THE URINE. 

of a not too concentrated solution of fuchsin. Since frequently 
only a small number of these casts occur, a number of prepara- 
tions must be made and each one carefully examined in order 
to be sure of their absence. These sediments are frequently 
accompanied by fat drops, pus, epithelium, blood, etc. 

Care is to be taken not to mistake for granular renal casts 
those mucous casts described in § 50, under mucus, which are 
frequently found in acid urine together with urates. (Plate 11. , 
fig. 2.) (Compare Mucus, § 50.)-=^ 

Concerning cancerous and tuberculous masses, see in the 
second part. 

§ 54. Spermatozoa. 

Spermatozoa appear under the microscope as spherical or 
nearly spherical elements, with a distinctly recognizable tail, 
which is usually pointed. They appear to have a spontaneous 
movement. We find them in the urine after masturbation or 
coitus, but they have been not unfrequently observed in the 
urine of typhoid-fever patients. 

It is very easy to find spermatozoa on account of their char- 
acteristic sha23e, which does not admit of their being confounded 
with anything else. At the same time spermatozoa are very 
indestructible, so that the diagnosis of semen in the urine is 
rendered still more easy. In order to find them it is necessary 
to place the urine at rest for a few hours at least in a conical 
glass (champagne glass), since the spermatozoa then sink to 
the bottom with the flakes of mucus. By carefully decanting, 
the greater part of the supernatant fluid is removed and a drop 
of the sediment in the apex of the glass is placed under the 
microscope. If spermatozoa are present they appear in the 
above-mentioned tadpole - shaped form. To detect them a 
magnifying power of from three to five hundred diameters is 
necessary. They soon lose their power of motion in pure 
water, and in urine also, especially when strongly acid or alka- 
line ; the spermatozoa at the same time undergo a peculiar 

"■ C. L. Rovida, Uebor das Wesea dor Harney Under. Jahresbcricht u. d. 
Fortschritte d. Thicrcliemic von R. Maly, 1872, p. 184 und 187. 

H. Senator, Ueber die im Harn vorkommenden Eiweisskorper und die Be- 
dingungen ibres Auftretens bei den verscbiedenen Nierenkrankbeiten, iiber 
Harney] inder und Fibrinaussebwitzung. Vircbow's Arcbiv, Band 60, p. 476. 



UBTNAUY SEDIMENTS. 187 

change of shape : they form hooks (Oesen) by the posterior 
part of the organism being bent forward like a loop, or coiled 
around the forward part. Moreover, the observation of Leh- 
mann is worthy of mention, viz., that urine containing semen 
very readily becomes alkaline, and shows in the mucous sedi- 
ment, even when few spermatozoa are found, peculiar, fine, 
laminated, very transparent flakes. 

Clemens has several times observed the passage of immature 
semen with the urine ; this consists of those seminal cells, in 
which the spermatozoa still lie in the envelope with head and 
tail attached to it ; these spermatozoa seldom showed any 
movement, such as is familiar in mature semen. Together Avith 
these sperm-cells Clemens often saw in the urine of patients 
suffering from spermatorrhoea spherical cells of 0'0033 to 0*005'" 
diameter filled with fine granules, which were mostly located 
on one side of the cell. These cells are nothing more than the 
mother cells of the spermatozoa. These elements are found 
chiefly in the last drops of urine passed by patients badly 
afflicted with spermatorrhoea, and also in those suffering from 
typhoid fever.* 

§ 55. Fungi. Infusokia. 

Fungi and infusoria are observed under the microscope in all 
urine which has stood for a long time ; they are found also in 
fresh urine which has already begun to decompose in the blad- 
der, as is quite frequently the case in catarrh of the bladder. 

The infusoria are usually very small. Most frequently punc- 
tiform monads or vibriones arranged like strings of pearls and 
often branched are found, and are especially abundant in urine 
containing mucus or albumen after standing awhile. Accord- 
ing to the investigations of L. Daille,t living vibriones very 
frequently occur in pathological freshly passed urine, in which, 
according to the form, size, and sort of movement, six different 
Varieties may be distinguished. The smallest of these vibriones 
are yo^oT) j the largest ^^77 mm. in size. They do not occur in 
the urine of all sick persons. Daille, however, claims to have 

* Canstatt's Jaliresbericlit, 1860, p. 285. 

f Journ. d. Pharm. et de Cliim., 1865, II., 450 ; also Wittstein's Vierteljalires- 
schrift, Band 16, p. 67, 



188 AI^ALYSIS OF THE UBmE. 

found tliat the urine of patients affected with lung diseases 
constantly shows such infusoria either directly or a short time 
after passing. I must also remark, that according to Hallier,* 
very different forms of fungus, such as vibriones and lepto- 
thrix-formations, have been frequently described as bacteriae 
and monas crepusculum, especially by Pasteur. Hassall ob- 
served a second sort of infusoria occurring in the urine, the 
Bodo urinarius. The living moving individuals are oval or 
round, yyVo" loiigj and 30V0" broad, gTanular and similar to 
mucous cells. Some times they are broader at one end and 
furnished at different points with one, two, or three threads or 
ciliaB. They increase by division. Among those described, 
they have, according to Hassall, most resemblance to the Bodo 
intestinalis. (Ehrenb.) They are said to occur very frequently 
in albuminous urine together with vibriones. 

Of spores, the urinary fermentation spore is very frequently 
found in the form of round or oval nucleated cells, which spring 
especially from the decomposed mucus. These fermentation 
spores lie at times isolated and at times aggregated together 
forming rows and groups. (Plate II., fig. 2 and 4.) In the 
advanced stage of fermentation they frequently accompany the 
sediments of urates, free uric acid, and calcic oxalate. 

According to von Tieghem the alkaline fermentation of urine 
depends on the development of a Torulacea, which consists of 
spherical non-granular cells arranged in rows like a rosary, and 
showing no positively recognizable distinction between envelope 
and contents ; they are 0*0015 mm. in diameter. This ferment 
appears to increase by budding, and never develops on the 
surface of the fluid, but either within it or on the bottom of 
the vessel, where it finally forms a white deposit mixed with 
the separated salts. According to Hallier t in the ammoniacal 
fermentation only the so-called nucleated cells are active, for 
when he sprinkled boiled healthy human urine with the spores 
of penicilium, there developed from the swarms only so-called 
nucleolar cells in incredible numbers. 

The oval transparent yeast spores which form during the fer- 
mentation of diabetic urine, are considerably larger than the 

* Hauler's Qahruugsersclieinungen, Leipzig, bei W. Engelman, 1867, p. 5, 66, 
etc. 
f Log. cit., p. 64. 



UBIXARY SEDIMEJS^TS 



189 




above, and in form and development correspond to tlie ordinary 
yeast cells. Tlieir form is usually somewhat oblong, sometimes 
also round, tlieir size is variable ; all have a distinct round nu- 
cleus which often appears like a hole. According to Hallier 
spores also form in the bladder, especially leptothrix chains, 
from which the yeast fungus may form even within the bladder in 
diabetic urine. On the surface of old ^m. 5. 

diabetic urine forked, branched, con- 
fervse threads containing spores fre- 
quently form, which after the urine has 
stood a long time often make such a 
thick maze that they cover the entire 
field. (Fig. 5.) It is asserted by Hallier 
and others that these more highly or- 
ganized fungi may under favorable con- 
ditions spring from the yeast cells, but 
this is j)ositively denied by De Bary and Eeess."^ Besides those 
mentioned, Hassall has found other forms of fungi in alkaline 
albuminous urine. 

Finally, the discovery of Letzerich is worthy of notice t that 
more or less considerable masses of fungi, spores, and mycelium 
occur in the urine in diphtheritis. The mycelium was bedded 
in finely granular, somewhat yellow-colored masses of exuda- 
tion, which floated in the urine and made it faintly cloudy. 

Urinary Sarcince have been found again by Ph. Munk in the 
urine of a man forty-three years old. The freshly passed urine 
Yjq q had a constantly alkaline reaction, it 

was cloudy, and contained a little albu- 
men. Under the microscope, in ad- 
dition to the epithelium, a few blood 
and pus corpuscles, vibriones, andtrij^le 
phosphate, and a large number of clear 
white cubes of sarcinse, rounded a little 
on the corners, were found. (Fig. 6.) If 
the urine stood for a while, a very 
abundant whitish deposit soon formed, 
which consisted chiefly of sarcinae and the other bodies men- 




" M. Reess, '' Die Alkoliolgaliningspilze," Leipzig, 1870. bei Arthur Felix, 
f Vircliow's Archiv, Band 52, p. 233. 



100 AJSfALYSIS OF THE UBINE, 

tioned, and especially in tlie months of May and June occupied 
a fifteenth or a twentieth part of the whole height of the daily 
amount of urine when emptied into a glass. In the autumn 
months the sarcinae decreased, and at the end of October were 
almost gone. 

Munk found single sarcinge elements and cubes formed of 
eight, sixty-four, and five hundred and twelve elements. Frag- 
ments of larger cubes were found, especially from those con- 
sisting of five hundred and twelve elements, in addition to the 
above forms. The single elements had a magnitude of 0*0008 
to 0*0016 mm.; the cubes consisting of eight elements had a 
breath of from 0*0016 to 0*0034 mm.; those consisting of sixty- 
four element, a diameter of 0*0032 to 0*006 mm.; while those 
consisting of ^nq hundred and twelve elements had a diameter 
of from 0*008 to 0*012 mm. The sarcinae from the urine were 
considerably smaller than the sarcinae from the stomach. The 
only form of sarcinae which can be indubitably recognized is 
that of the cube described by Virchow, which is especially well 
seen when the preparation is made to roll under the microscope. 
No tables or plates were to be seen. The reaction of the urine 
appears to have no influence on the development of sarcinae ; 
in this case it was constantly alkaline, in the one observed by 
Welker it was acid, in others occasionally neutral."^ 



V. ACCIDENTAL CONSTITUENTS. 

§ 56. 

This section embraces the changes which substances undergo 
on their passage into the urine. The importance of the study 
of these changes is at once apparent, since it gives us an in- 
sight into the complexity of the metamorphosis in the animal 
organism. Yet to obtain uniformly good results in this respect 
naturally a very great series of investigations are necessary, 
which must be accurately carried out even to the most minute 
detail, and indeed best by the assimilation of organic bodies 
whose chemical composition is perfectly known, and whose pro- 
ducts of decomposition have been accurately investigated in all 

•"" Archiv f. path. Anat. u. Physiol., Band 22, p. 570. 



ACCIDENTAL CONSTITUENTS OF URINE. 191 

directions, because from the changes which such compounds 
suffer in the economy conclusions may be drawn concerning 
the chemical processes which are at work in the organism, and 
especially in the blood, in the metamorphosis of tissue. 

Before passing to the individual substances the following 
facts are to be mentioned : 

In general it is self-evident that only those substances can 
pass into the urine which, in the first place, do not serve as 
food, and secondly, are soluble in water and have no tendency 
to form insoluble compounds with the organic or inorganic 
constituents of the body. For these reasons, therefore, it is 
quite easy to find most of the soluble alkaline salts again un- 
changed in the urine. But if we introduce into the body a 
non-oxidized material which has a tendency to take up oxygen, 
we find it in the urine again oxidized ; such a body, for ex- 
ample, is sulphide of sodium, which always appears in the 
urine in the form of sulphate of sodium. But all substances 
which form insoluble or difficultly soluble compounds with the 
constituents of the body, as for example, most metals which 
unite with the protein matters as Orfila has found, only appear 
in the urine again when they have been supplied to the econo- 
my in very large amount. 

Many organic bodies, moreover, suffer in the organism simi- 
lar or the same changes which we are able to bring about ar- 
tificially by the action of permanganate of potassium or ozone, 
in neutral or alkaline solution. Others again become so com- 
jDletely oxidized that it is not possible to detect either them or 
the products of their decomposition in the urine, while many give 
off oxygen and appear in the urine as lower stages of oxidation. 

Lastly, the length of time is to be observed which is required 
for the elimination of a substance with the urine. It may be 
assumed as a rule, that readily soluble substances will be 
quickly removed again from the body with the urine, yet indi- 
viduality appears to exercise some influence in this respect ; 
thus, Lehmann has observed that after a dose of ten grains of 
iodide of potassium no trace of iodine can be found in the urine 
in many persons twenty-four hours afterward, while in others 
it will be found often three days afterward. 

We will now consider the behavior of different substances in 
the economy. 



192 ANALYSIS OF THE URINE. 



I. Inoeganic Substances, 



A. Salts of the Heavy 3Ietals. 

Since the salts of the heavy metals form difficultly soluble 
compounds with many animal matters, especially the protein 
bodies, they only appear in the urine again when they have been 
taken into the economy in large doses. Orfila found antimony, 
arsenic, zinc, gold, silver, tin, lead, and bismuth in the urine 
after large doses, while they can at other times only be found 
in the liver and its secretions and the solid excrements, when 
they are given in relatively small and frequently repeated 
doses. 

Iron, after its internal administration, can frequently be de- 
tected immediately in the fresh urine by the ordinary reagents. 
(Lehmann.) 

Arsenic, according to Eoussin, is said to exist in the urine as 
ammonio-magnesian arseniate. Lead was directly detected by 
Moos in the urine, by means of sulphuretted hydrogen, on the 
third day after a daily dose of from eight to nine grains. 

To detect the heavy metals in the urine the same methods 
are to be followed which are adopted in legal cases to discover 
them in presence of organic matters. I therefore content myself 
with referring to Fresenius's guide to qualitative analysis. 

3Iercury. Recently, electrolysis has frequently been success- 
fully employed to detect mercury in the urine, and on account 
of the importance of this subject the method made use of by 
Schneider for this purpose may be mentioned here. Five grams 
of chlorate of potassium are dissolved in one liter of the urine 
to be examined, hydrochloric acid is added until the reaction 
is strongly acid, and then it is heated on the water bath. If 
the color becomes dark during the evaporation, a fresh amount 
of the oxidizing medium is to be added, but the heat is to be 
continued until a specimen after the addition of hydrochloric 
acid has no bleaching action on coloring matters. On the con- 
trary, it is no advantage to continue the evaporation of the 
urine until the salts crystallize out, since the fluid becomes 
colored dark when concentration is pushed to this point. Be- 
sides, such highly concentrated solutions are not well fitted for 
electrolysis, as Schneider has convinced himself by many experi- 



ACCIDENTAL CONSTITUENTS OF URINE. 193 

ments. In most cases very large amounts of urine are neces- 
sary. Schneider took the entire quantity of urine passed during 
from three to six days (seven to fifteen liters) for his experi- 
ments. After the addition of chlorate of potassium and hydro- 
chloric acid it was concentrated on the water bath to one-seventh 
or one-eighth of its volume. Schneider used for the electrolysis 
of the fluid thus prepared a Smee's battery of six elements 
(other constant chains are naturally quite as efficient), whose 
anode consisted of a platinum plate four centimeters broad, and 
whose cathode was a gold wire one millimeter thick, which 
terminated in a club-shaped thickened end two millimeters in 
diameter. For the purpose of confining the division of the 
mercury to the smallest surface possible the electrolysis was 
performed in a vessel whose breadth was greater than its height. 
The electrolysis was continued eighteen to twenty-four hours. 
The gold thread, which at the end of the experiment appears 
to be amalgamated when mercury is present, is tested as fol- 
lows: It is put into a carefully cleaned glass tube which is 
drawn out to a capillary point at one end, and the tube is then 
closed at the other. The broad portion of the tube which con- 
tains the metal is heated to a red heat throughout its entire 
length. If a sublimate is deposited on the cool part of the tube 
after about five minutes, it is driven by heating into the capil- 
lary portion, and then the metal is once more heated in order 
to ascertain if a new sublimate appears. Now that part of the 
tube which contains the metal is melted from the capillary end, 
so that a short piece of the wide portion remains behind as a 
flask-like dilatation. After cooling the dilated end is opened 
by nipping off the capillary end, then a little iodine is intro- 
duced into it by means of a glass thread, and it is again closed 
by heat. The iodine vapor is thus driven into the capillary 
part of the tube which contains the mercury and disappears ; 
in its place brown, red, or yellow rings appear, according to 
the amount of iodine introduced. If the brown rings are very 
carefully heated, the iodine evaporates from them, and red 
rings of mercuric iodide remain. The red as well as the yellow 
rings volatilize on being strongly heated, but immediately de- 
posit again on the cold portions as a red sublimate, but which 
under certain circumstances may be yellow. The yellow rings 
consist of mercurous iodide ; they occur when the amount of 
13 



194 'ANALYSIS OF THE URINE. 

iodine wliicli was added was insufficient to form mercuric iodide ; 
if another small crystal of iodine is put into the capillary end, 
and heated, the yellow rings readily become red. Under the 
microscope the red crystals appear as four-sided octahedra, 
which are often so placed with their surfaces toward each other 
that they produce feathery crystals resembling those of am- 
monic chloride. 

No mercury could be detected by electrolysis in three cases 
in which the urine abounded in iodide of potassium, and which 
after the addition of chlorate of potassium and hydrochloric 
acid was concentrated to one-tenth. After these urines, how- 
ever, were treated with sulphuric acid, which contained nitrous 
acid and were evaporated on the water bath until the iodine 
was completely removed, the cathode on repeating the electro- 
lysis showed distinct traces of amalgamation, and the subse- 
quent heat tests showed the most distinct reaction for mercury. 
It appears advisable, therefore, in urine which contains iodides 
to first free it from its iodine. This is easily done by heating 
on the w^ater bath and gradually adding sulphuric acid which 
is saturated with nitrous acid. 

Mayencon and Bergeret "^ use the following simple method to 
detect mercury, which, however, is noL in every case certain: 
An iron nail is suspended in the urine which is to be examined 
by means of a platinum wire, then pure sulphuric acid is added 
until oxygen is slowly evolved. The mercury now forms a 
metallic deposit on the platinum wdre. After about half an 
hour the wire is removed, washed, and then exposed to the 
vapors of chlorine to convert the mercury into corrosive subli- 
mate. If the platinum wire is then gently drawn over a piece 
of filter paper which has been moistened with a one per cent, 
solution of iodide of potassium, a red streak of mercuric iodide 
is obtained, which dissolves in an excess of iodide of potassium. 

Kletzinsky evaporates the urine which has been treated with 
chlorate of potassium and hydrochloric acid to dryness, and 
extracts the residue with ether to remove the corrosive subli- 
mate. This procedure, according to Schneider, is very uncer- 
tain, since some mercuric chloride combined with the alkaline 



" Chem. Centralblatt, 1873, p, 678. Zeitsclir. f. analyt. Chem., Band 13, p. 
103. 



ACCIDENTAL CONSTITUENTS OF URINE. I95 

clilorides in the form of double chloride is retained in the resi- 
due. These compounds are nearly insoluble in ether, and there- 
fore no sublimate can be dissolved out by ether from the eva- 
porated residue of the urine when completely dried. On ac- 
count of the importance of this subject I give here the results 
obtained by Schneider : 

1. In the urine of syphilitic patients who had never been sub- 
jected to treatment by mercury, no mercury could be detected 
by electrolysis. 

2. The same negative result was obtained on testing the urine 
of individuals who had pursued a mercurial treatment a long 
time before. The investigations were commenced on different 
persons, fourteen days, five months, and half a year after the 
mercurial treatment. 

3. The urine constantly contains mercury during the internal 
use of mercurial preparations. 

4. The experiments of Schneider are by no means favorable to 
the views now quite generally entertained of the action of iodide 
of potassium on metals which are retained within the organism. 
In three cases where iodide of potassium was given immediately 
after treatment by corrosive sublimate this remedy distinctly 
did not increase the separation of mercury with the urine. 

5. In a case of hydrargyrosis which ended fatally the urine 
abounded in mercury, though only 1,400 cc. could be obtained 
for examination. Also the brain and especially the liver con- 
tained it."^ 

Thallium. According to W. Marme thallium is readily de- 
tected by electrolysis in the urine after the latter has been 
treated with chlorate of potassium and hydrochloric acid and 
afterward concentrated. The metal fixed in this way on a 
platinum wire and carefully cleansed with distilled water is 
brought directly into the flame of the spectral apparatus, but in 
this case the anode as well as the cathode is to be tested, t 

Cadmium is detected also by electrolysis of the urine after 
being treated with chlorate of potassium and hydrochloric 
acid.:}: 

* Schneider, iiber das chemisclie und electrolytisclie Verlialten des Quecksilbers 
in tliierischen Substanzen. Wien in Commission bei K. Gerold's Sohn, 1860. 
t Zeitscbrift f. analyt. Cbem., Band 6, p. 503. 
;[: Zeitscbrift f. analyt. Cbem., Band 6, p. 298; 



196 ANALYSIS OF THE UBINE. 

B. Free 3Iineral Acids. 

According to the investigations of C. Gaethgens^ dilute sul- 
phuric acid after long use goes over into the urine partly in an 
uncombined state. 

C. Salts of the Alkalies. 

1. Carbonates of the alkalies always appear again as such in 
the urine, although a portion is necessarily neutralized by the 
free acid of the gastric juice. They render the urine either 
neutral or alkaline. Free carbonic acid, sparkling wines, beer, 
and acid alkaline carbonates cause an increased excretion of 
calcic oxalate, and at the same time increase the amount of 
free carbonic acid in the urine. 

2. Lithium salts, after their internal use, very readily go over 
into the urine. 

To detect the lithium a sufficient amount of the urine to be 
examined is evaporated to dryness and the residue heated at a 
moderate temperature to complete ignition. After cooling, the 
carbon is extracted with dilute hydrochloric acid, filtered, the 
colorless filtrate evaporated to dryness, treated with strong alco- 
hol, filtered, the alcoholic solution evaporated to dryness, and 
the residue now left is tested with the spectroscope. I have 
always succeeded in detecting lithium, after its internal use, 
with absolute certainty according to the above method. 

3. Ammonium salts pass into the urine in part unchanged. 

I have made experiments on this point with a young man 
twenty years of age, who passed on an average of twelve deter- 
minations 0'6137 grams of ammonia in twenty-four hours, cor- 
responding to 1*9305 grams of ammonic chloride. Of a solu- 
tion, which in ten cc. contained exactly two grams of ammonic 
chloride, ten cc. were taken in the evening in a glass of water, 
the urine was collected for exactly twenty-four hours and sub- 
mitted to analysis. The experiments were continued for five 
days, and during this time, if we deduct the above-mentioned 
normal amount, 9*957 grams of ammonic chloride were elimi- 
nated again instead of the ten taken. 

4 Ferrocyanide of potassium appears in the urine reduced 
to the ferricyanide. 

5. Sulphocyanide of potassium appears quickly in the urine 
even after taking small amounts. 

* Centralblatt f. d. med. Wissenschaft., 1872, No. 53. 



ACCIDENTAL CONSTITUENTS OF URINE. I97 

6. Alkaline silicates, chlorates, and borates are found again in 
tlie urine. 

7. Perchlorate of potassium, according to Kabuteau, readily 
appears in the urine. 

To detect it the urine is completely precipitated with nitrate 
of silver, the excess of silver is removed from the filtrate by 
sodic hydrate, filtered again, evaporated to dryness, and the 
residue ignited. The perchlorate of potassium present thus be- 
comes converted into the chloride of potassium, whose amount 
can easily be determined in the usual way.^ 

8. Iodide of potassium also passes into the urine and is 
readily detected by the familiar starch reaction. 

Pierre Scivoletto moistens strips of filter paper with starch 
paste, sprinkles them after drying with the urine to be tested 
for iodine, and then suspends them in the upper part of a flask, 
at the bottom of which there is a little fuming nitric acid. If 
iodine is present, the sprinkled spots become colored blue. 
The following method used by Castain might be more accurate 
when' very small amounts of iodine were present : About one 
liter of the urine is treated with two grams of caustic potash, 
evaporated to dryness, and all of the organic matter ignited. 
The residue is dissolved in water and tested for iodine with 
starch and chlorine water or fuming nitric acid. 

A concentrated solution of hyponitric acid in sulphuric acid 
is suitable to free the iodine. Or it may be set free by the care- 
ful addition of bromine water, and removed by shaking with 
bisulphide of carbon. I prefer the last reaction to all others. 

9. Bromide of potassium passes into the urine readily. 

To detect it the residue of the urine is carefully but com- 
pletely carbonized. The carbon is extracted with water, the 
bromine present in the colorless filtrate is freed by a drop of 
chlorine water, and the mixture shaken with ether or bisul- 
phide of carbon in the usual manner. For the quantitative es- 
timation Caigniet uses a standard solution of hypochlorite of 
sodium. The colorless filtrate is acidulated with citric acid 
and the standard solution carefully added from a burette. 
The freed bromine is taken up with bisulphide of carbon which 
is renewed from time to time. A colorless fluid always results, 

* Zeitsclirift f. analyt. Chem., Band 8, p. 233. 



198 ANALYSIS OF THE URUSTE. 

and it is easy to liit the point at which another drop of the 
hypochlorite of sodium solution causes no more coloration of 
the fluid and of the bisulphide of carbon, by which the end of 
the experiment is indicated.^ 

10. Sulphide of potassium escapes again partly as sulphate, 
and partly unchanged. 

D. Salts of the Alkaline Earths. 

1. Soluble barium salts can be detected in the urine when 
they have been taken in pretty large doses. 

2. Lime salts do not pass into the urine at all, or at most only 
in very small amount. On the contrary, S. Soborow t observed 
a considerable increase in the amount of lime in the urine after 
large doses of the carbonate (8 to 10 grams in a day). After 
taking eight grams of carbonate of calcium the amount of lime 
in the urine increased from 0*216 to 0'73 grams, and after the 
internal use of ten grams of the carbonate there was an in- 
crease of 0*27 to 0*87 grams. An increase of lime in the urine 
was also obtained in a dog after the subcutaneous injection of 
one gram of the acetate of calcium. 

3. Magnesium salts are partly eliminated with the urine. 
(Kerner.) 

II. Organic Substances. 

A. Free Organic Acids. 

1. Organic acids, such as oxalic, citric, malic, tartaric, and 
gallic acids, according to Wohler, pass into the urine unchanged 
when they are presented to the economy in a free state. 

2. Acids of the Aromatic Series. 

a. Benzoic acid becomes converted into hippuric acid in the 
economy by combining with a molecule of glycocoll and elimi- 
nating a molecule of water. 

f^3^a, + €,H5N02=€9H3Na3 + H.O 
[C,,HeO, + C,H,NO,= C^sH^NOe + 2H0] 
(Benzoic acid) (Glycocoll) (Hippuric acid). 

Benzoic ether, oil of bitter almonds, cinnamic, quinic, and 
mandelic acids are also transformed into hippuric acid, and 

* Zeitschrift f . analyt. Chem., Band 9, p. 427. 

f Centralblatt f. d. med. Wissenscliaf t. , 1872, Nr. 39. 



ACCIDENTAL CONSTITUENTS OF UEINE. 199 

appear as such in the urine. (Frerichs and Wohler ; Erdmann 
and Marchand; Lautemann; O. Schultzen, and C. Griibe.) 

Nitrobenzoic acid yields nitrohippuric acid. (Bertagnini) 
Chlorobenzoic acid yiekls chlorohippuric acid. (O. Schultzen 
and C. Grabe.) 

b. Toluic acid (/3) appears in the urine as toluric acid (Kraut) ; 
salicylic acid in part as salicyluric acid (Bertagnini); anisic 
acid as anisuric acid (O. Schultzen and C. Grabe). These acids 
stand in the same relation to the original that hippuric acid 

does to benzoic. Also, after the internal use of mandelic acid, 
a hippuric acid, corresponding to mandelic acid, appears in the 
urine. (O. Schultzen and Grabe.) 

c. Experiments with phtalic, amidobenzoic, cuminic, and cu- 
marinic acids led to no decided results. 

d. Oxybenzoic and paraoxybenzoic acids, the known isomers 
of salicylic acid, according to the investigations of Maly ''^ do not 
take up simple giycocoll in the organism, but methyl- or ethyl- 
glycocoll, and then appear in the urine as methylated or ethyl- 
ated hippuric acid. 

e. Salicylic acid, as already mentioned above, goes over only 
in part as salicyluric acid, another part passes from the economy 
unchanged. After the internal use of 0*3 gram of salicylic acid 
it could be detected in the urine in two hours, but was still 
present after twenty hours. (Kolbe.) 

To test urine for unchanged salicylic acid it is treated with 
a solution of ferric chloride drop by drop. The first drop of 
an iron solution always causes an abundant separation of white 
phosphate of iron, but as soon as this is precipitated the in- 
tense violet reaction with salicylic acid appears on further ad- 
dition of the iron salt. 

O. Schultzen and C. Grabe t from their investigations of this 
subject draw the conclusion that all aromatic acids in which 
the group €H02 directly replaces one atom of hydrogen in ben- 
zol, are transformed in the economy to the corresponding hip- 
puric acid, while in those acids which contain a complicated 
side chain, as cinnamic and mandelic acids, this side chain 
becomes oxidized, so that the hippuric acid corresponding to 

* Jaliresbericlit lib. d. Fortscliritte der Thiercliemie, 1872, p. 137. 
f Annalen d. Cliemie u. Pharm., Band 142, p. 345. Reichert's und Du Bois- 
Reymond's Arcliiv, 1867, Heft 2. 



200 ANALYSIS OF THE JJRINE. 

the one ingested does not appear in the urine, but that corre- 
sponding to the product of its oxidation; consequently all 
aromatic acids yield in the economy so-called hippuric acid, 
that is, glycocoU substitution products. 

3. Pyrogallic acid, which, according to G. Jiidell,* in large 
doses has an intensely poisonous action, goes over into the urine 
undecomposed. 

4 Tannic acid is changed to gallic acid and appears as such 
in the urine. 

5. Camphoric acid is eliminated unchanged with the urine. 

6. Succinic acid was found again in the urine. (Meissner and 
Shepard.) 

Considerable amounts of succinic acid occurred after par- 
taking largely of asparagus. Here it was evidently formed by 
the decomposition of the asparagin (amidosuccinaminic acid) 
in contact with ammonia. 

7. Uric acid undergoes the same decompositions in the econo- 
my which we are able to produce artificially by the action of 
peroxide of lead, or better still, of permanganate of potas- 
sium. In the perfectly normal organism, when the respiration 
is unimpeded, uric acid is decomposed by the absorption of 
water and oxygen for the most part into urea and carbonic 
acid. 

When the respiration is more or less disturbed, oxalic acid 
accompanies the above products of decomposition, and under 
certain circumstances allantoin also, which Stiideler and Fre- 
richs saw really occur in artificially disturbed respiration. (See 
Uric Acid, § 6, D, 3 and 5.) 

8. After taking abietic acid or other resins, such as turpen- 
tine, balsam copaiba, etc., according to Maly, abietate of sodium 
is eliminated with the urine. In such a urine a white cloudi- 
ness, not unlike a precipitation of albumen, is produced by nitric 
acid, which, however, immediately disappears on the addition 
of alcohol. 

B. Indifferent Substances. 

1. Alcohol. According to the investigations of Lieben,t al- 
cohol is constantly eliminated in the urine after partaking of 
spirituous drinks, and can be separated by fractional distilla- 

* Hoppe-Seyler, Med. chem. Untersuchungen, Heft :^, p. 422. 
fAunal. d. Chem. u Pharm,, 7, Supplementbd. , p. 236. 



ACCIDENTAL CONSTITUENTS OF URINE. gQl 

tion, yet the amount of alcohol which appears in the urine is 
always relatively small, both after small and large doses. 

2. Phenol (carbolic acid) appears in the urine after both its 
external and internal use, and, according to Waldenstrom and 
Almen, Salkowski, and others, may be readily detected in the 
distillate of the urine acidulated with sulphuric acid by means 
of the usual reactions.-^ It is well to shake the distillate ob- 
tained with ether, evaporate the ether, and test the residue for 
phenol. (§ 9, C.) 

3. Chloroform is eliminated with the urine, and such a urine 
reduces Fehling's copper solution on heating. To detect and 
estimate it quantitatively, according to Marechal, a stream of 
air is forced through the urine to be examined, and, saturated 
with chloroform, is conducted through a red-hot porcelain tube. 
The chlorine, which by this process is set free from the chloro- 
form, will precipitate chloride of silver on being passed through 
a Liebig's bulb tube filled with nitrate of silver solution, and 
from the weight of the chloride the amount of chloroform which 
was present may be calculated. t 

4. Chloral, according to the investigations of von Mering and 
Musculus,:|: is eliminated unchanged in the urine to a very small 
extent, but by far the greatest part combines with constituents 
of the economy, and appears in the urine as urochloralic acid 

(0:H,,C],ae.) 

After taking chloral (^yq to six grams) the urine has a strong 
acid reaction and reduces an alkaline solution of copper. The 
detection of chloroform or formic acid in the urine did not suc- 
ceed, but on the other hand small quantities of chloral were 
detected by means of Hofmann's isocyanphenyl reaction. Sugar 
was not present, but a not inconsiderable amount of an organic 
acid which turned a ray of polarized light to the left, and to 
which von Mering and Musculus have given the name urochlo- 
ralic acid, was detected. 

Urochloralic acid is separated by the following treatment: 
The urine containing chloral is evaporated on the water bath, 
treated with sulphuric acid, and shaken with a mixture of two 
volumes of ether and one volume of alcohol. The ether is dis- 

* Zeitschrift f. analyt. Chem., Band 10, p. 125. 

f Zeitschrift f. analyt. Chem., Band 7, p. 393 und Band 8, p. 99. 

X Berichte d. deutsch. cliem. Gesellscliaf t, Band 8, p. 662. 



202 ANALYSIS OF THE URINE. 

tilled off, the residue neutralized with potassic hydrate, evapo- 
rated, taken up with 90 j)er cent, alcohol, filtered, the filtrate 
precipitated with ether, the precipitate dissolved in water, 
decolorized with animal charcoal, and evaporated to a small 
volume. On cooling a crystalline mass separates, which for the 
most part consists of the potassium salt of urochloralic acid. 
By washing the salt, which has been dried over sulphuric acid, 
with absolute alcohol, it is freed from the urea and hippurate of 
potassium which are mixed with it. The pure potassium salt 
is then dissolved in as little water as possible, acidified with 
hydrochloric acid, this solution shaken with the mixture of 
ether and alcohol above mentioned, and filtered. Most of the 
chloride of potassium remains on the filter, and the rest sepa- 
rates if the filtrate is treated with a great excess of ether, and is 
allowed to stand forty-eight hours. The filtrate is evaporated 
and the residue freed from chlorine by moistened oxide of silver. 
The excess of silver oxide which has gone into solution is 
quickly precipitated by sulphuretted hydrogen, and the filtrate 
evaporated to a syrupy consistence. The acid crystallizes after 
twelve hours. The potassium salt gave 12 '56 per cent, of potas- 
sium ; the barium salt 19*57 per cent, of barium. 

Urochloralic acid crystallizes in colorless silky needles, which 
have a starlike arrangement like tyrosin, and readily dissolve 
in water, alcohol, and a mixture of alcohol and ether, but are 
insoluble in ether. On boiling it reduces an alkaline solution 
of copper, silver, and bismuth, and colors yellow a solution of 
indigo made feebly alkaline with carbonate of sodium. Its so- 
lution turns the plane of polarization toward the left, and in- 
deed the specific power of rotation of the potassium salt for 
yellow light was found to approximate (<^') = —60^ The urine, 
after the introduction of five to six grams of chloral hydrate 
into the organism, turned polarized light about 5"" to the left; it 
contained, therefore, about ten grams of this acid in the liter. 
Urochloralic acid on heating with anilin and an alcoholic solu- 
tion of potassic hydrate evolved no isocyanphenyl. 

5. Hydrocarbons of the Benzol Series.^ 

a. Benzol is oxidized in the system and appears in the urine 
again as phenol (carbolic acid). 

* 0. Sclinltzeu u, B. Naunyn, Reichert's u. Du Bcis-Reymond's ArcMv, Jalirg. 
1867, Heft 3. 



ACCIDENTAL CONSTITUENTS OF URINE. 203 

b. Toluol is oxidized to benzoic acid in the economy, and 
appears in the urine as hippuric acid. 

c. Xylol in the system is first oxidized to toluylic acid, and 
appears in the urine as toluric acid. 

d. Camphor cymol (GjoHu) after its internal administration is 
converted into cuminic acid (propylbenzoic acid) according to 
the investigations of Nencki and Ziegler."^ 

To separate these acids the urine is treated with an amount 
of subacetate of lead which is insufficient to completely precipi- 
tate it, it is filtered, the filtrate concentrated to a syrup, pre- 
cipitated with alcohol, the alcoholic solution evaporated, acidu- 
lated with dilute sulphuric acid, and shaken with ether. The 
ether leaves an acid oil behind, which solidifies after long stand- 
ing. It is saturated with carbonate of barium, treated with 
animal charcoal, and the concentrated filtrate treated with hy- 
drochloric acid, which separates the acid in crystals which are 
purified by re crystallization. 

e. Mesitylen (trimethylbenzol), according to Nencki,t readily 
becomes converted into mesitylenic acid in the economy, and is 
eliminated in part as such, and in part united with glycocoll 
as mesitylenuric acid. Both can be separated by distillation 
with aqueous vapor, during which the volatile non-nitrogenous 
acid passes over and deposits in the receiver. 

f. Nitrotoluol has an excessively poisonous action. Parani- 
trotoluol, which in dogs, at least, manifests no poisonous action, 
becomes paranitrobenzoic acid to a very slight extent, and is 
found in the urine as such. The largest part of the paranitro- 
toluol, on the other hand, is transformed into paranitrohippuric 
acid and appears in the urine as paranitrohippurate of urea. 
(Jaffe.)t 

C. Salts of the Organic Adds. 

1. Neutral salts of the alkalies with the vegetable acids are 
oxidized in the economy just as if they were consumed in oxy- 
gen gas. They appear in the urine as carbonates, therefore, 
render it alkaline, cause an effervescence with acids and a sepa- 
ration of the earthy phosphates. If the salts at the same time 



* Berichte der deutscla. cliem. Gesellscliaft, 1872, p. 749. 
f Arcliiv f . experim. Patliol. u. Pharmakoi. , 1873, p, 420. 
X Berliner Berichte, Band 7, p. 1673. 



204 AI^ALYSIS OF TEE URmE. 

have a purgative action, or if they are taken with much animal 
food, the urine in the former case is often not at all, and in the 
latter only slightly alkaline. Moreover, other circumstances, 
especially certain diseases, exercise an influence on these ordi- 
nary appearances. 

2. The ethereal sulphates of sodium, according to the investi- 
gations of E. Salkowski,"^" pass over into the urine unchanged. 

Para- and meta-sulphophenate of sodium likewise leave the 
economy unchanged. After the internal use of these salts the 
urine is colored deep blue after the addition of a trace of ferric 
chloride, as happens with phenolsulphuric acid. 

Benzol sulphate of sodium provoked much diarrhoea in dogs, 
and could not be detected in the urine. The urine contained 
benzolsulphuric acid unchanged after the injection of two grams 
under the skin. 

D. Organic Bases, etc. 

1. Quinine can be easily found in the urine after the admin- 
istration of not too small doses. 

a. According to the interesting investigations of Kerner,t 
quinine can be most easily and surely detected in the urine, 
even when diluted two million times, by means of its fluorescent 
properties. Since, however, the chloride of sodium which is 
present prevents the fluorescence, the chlorine must be re- 
moved first, which is done most efficiently by means of a con- 
centrated solution of mercurous nitrate. Twenty-five to fifty 
cc. of urine are treated with the reagent until a precipitate no 
longer takes place and there is a slight excess of the reagent 
present, it is filtered and the precipitate washed. Of the origi- 
nal color of the urine only a pale yellow is left, and when not 
too small amounts of quinine are present, the fluorescence can 
be perceived by daylight during the filtration. If the fluid is 
placed in the fluorescope constructed by Kerner and repre- 
sented in fig. 7, the fluorescence wdll be seen most beautifully, even 
at a dilution of two million times, as soon as the induction current 
passes through the Geissler fluorescence-tube, and the cover 
is closed, if the observation is made through the pyramidal 
tunnel. For the sake of comparison it is well to fill only one 

* Pfliiger's Arcliiv, Band 4, p. 91. 

f Arcliiv f. Pliysiologie, Band 2, p. 200. Zeitschrift f. analyt. Cliem., Band 
0, p. 134 im Auszug-. 



ACCIDENTAL CONSTITUENTS OF URINE. 205 

arm of the U-sliaped tube with the urinary fluid, and the other 
with water. The reaction is still more delicate if the urinary 

Fig. 7. 



fluid is completely decolorized before testing ; this is done most 
simply by conducting a few bubbles of sulphuretted hydrogen 
into it, when the sulphide of mercury takes up the rest of the 
coloring matter. 

Herapath gives the following method for the same purpose : 
The urine is rendered alkaline with a little potassic hydrate ; 
it is shaken with ether, which takes up the quinine, after which 
the ether is evaporated. Then a test fluid is prepared of three 
drachms of acetic acid, one drachm of rectified spirit, and six 
drops of dilute sulphuric acid. One drop of this mixture is 
put on a glass slide, a little of the ether residue is added to it, 
and then a very small drop of an alcoholic solution of iodine is 
brought in contact with it by means of a glass hair. If quinine 
is present, a cinnamon color appears immediately, caused by 
the iodide of quinine, and later sulphate of iodo-quinine is ob- 
tained, which is remarkable for its polarizing properties, and 
which is recognized under the microscope. Sulphate of iodo- 
quinine crystallizes in extremely thin plates, whose power of 
polarization is so strong that they can be used instead of tour- 
maline plates. Two plates as thin as gold leaf, when they cross 
each other at a right angle, allow no light to pass through.*^ 

* Journ. f. pract. Chem,, Band 96, p. 87. 



206 ANALYSIS OF THE URINE. 

According to Binz, quinine can be detected in urine, when 
present in the proportion of one part to 40,000 or 50,000 parts 
of urine, by means of a solution of two parts of iodine and one 
part of iodide of potassium in forty parts of water.'' 

b. By the method of Yitali and E. Salkowsld, the urine is 
made alkaline with ammonia and shaken with ether. After the 
addition of a drop of hydrochloric acid the ether is evaporated, 
the residue is dissolved in water, rendered ammoniacal again, 
and this solution shaken with ether a second time. The resi- 
due which now remains, after the evaporation of the ether, is 
used for the familiar reaction with chlorine water, and am- 
monia. 

2. Thein and theobromin cannot be detected again in the 
urine. 

3. Anilin was not found again by Wohler. 

4 Alloxantin, according to Wohler, appears to break up into 
urea and other substances. 

5. Allantoin does not pass into the urine ; it also causes no 
increase of the calcic oxalate, but is probably decomposed into 
carbonic acid and urea. 

6. Urea passes off with the urine again unchanged. 

7. Guanin causes a considerably increase of the urea, but in 
very large doses it passes off partly with the faeces. 

8. Glycocoll and leucin, even when taken into the economy 
in large doses, are eliminated again in the form of urea.f 

9. Sarkosin changes in the economy partly to methylhydantoic 
acid, and partly takes up the sulphamic acid group and appears 
in the urine as a body containing sulphur. Two well-charac- 
terized bodies appear in the urine after taking a sufficient 
amount of sarkosin, which, on heating with hydrate of barium, 
decompose into carbonic acid, ammonia, and sarkosin, or sul- 
phuric acid, ammonia, and sarkosin. (Schultzen.)J 

Schultzen obtained these compounds from the urine by the 
following procedure : The urine passed, within the next two 
hours after their ingestion was completely jDrecipitated by 
basic acetate of lead, the filtrate was shaken with oxide of sil- 

*Zeitschrift f. analyt. Chem., Band 9, p. 538. 

f 0. Scliultzen und Nencki. Bericlit d. deutsclien chem. Gesellscliaft, 1869, 
p. 5GG. 

X Berliner Bericlite, Band 5, p. 578. 



ACCIDENTAL CONSTITUENTS OF URINE. 207 

ver, it was filtered off from tlie excess of oxide and chloride of 
silver, and treated with sulphuretted hydrogen. The filtrate 
from the metallic sulphides was evaporated to a syrup, treated 
with dilute sulphuric acid in excess, and frequently shaken 
with large amounts of ether. The ether left a colorless syrup 
which contained both bodies. By boiling with carbonate of 
barium and precipitating the concentrated solution with abso- 
lute alcohol, the barium salt of the compound of sarkosin with 
sulphamic acid separates, while the alcoholic solution after 
evaporation leaves as a residue the carbamic acid derivative in 
magnificent tabular crystals as clear as glass. 

According to recent investigations by Baumann, von Mering,* 
and Salkowskijt sarkosin for the most part leaves the economy 
unchanged and appears as such in the urine again. But since 
methylhydantoic acid readily becomes methylhydantoin by the 
separation of water, Salkowski considers that the occurrence 
of this body in the urine is possible after taking sarkosin. 
Lastly, a part of the sarkosin (methylglycocoU) may be changed 
into methylurea, just as glycocoll changes into simple urea. 

Moreover, it must be mentioned that, according to the inves- 
tigations of Hoppe-Seyler and Baumann, methylhydantoic acid 
is readily formed, if sarkosin is warmed a long time with urea 
and an excess of baryta. 

Sarkosin can be detected in urine which has been first 
treated with basic acetate of lead, then freed from the excess of 
lead, evaporated, and fractional precipitation made with alcohol 
or rather a 'mixture of alcohol and ether. By treating with 
hydrate of copper, well-crystallized sarkosin-copper is produced. 
If this is dissolved in water to which has been added a drop 
of hydrochloric acid, the copper precipitated with sulj)huret- 
ted hydrogen, and the hydrochloric acid with oxide of silver, 
the filtrate yields crystals of sarkosin after evaporation. (Sal- 
kowski.) 

10. Taurin behaves in a similar manner in the economy. A 
small portion goes over into the urine unchanged, the largest 
portion takes up the carbamic acid group and appears in the 
urine as taurocarbamic acid, which crystallizes in shining quad- 



* Berichte d. deutsch. chem. Gesellschaft, Band 8, p. 584. 
f Bericlite d. deutscli. chem. Gesellschaft, Band 8, p. 638. 



208 ANALYSIS OF THE URINE. 

rilateral leaflets, and on being treated with baryta water at 130° 
or 140'' C. decomposes into carbonic acid, ammonia, and taurin. 
Tliis acid can be produced artificially from taurin and cyanate 
of potassium at a gentle heat. (Salkowski.)"^ 

To detect taurin in the urine it is precipitated with basic ace- 
tate of lead, filtered after standing several hours, the filtrate 
freed from lead with sulphuretted hydrogen, evaporated and 
precipitated with absolute alcohol. The alcohol is quickly 
poured off from the precipitate which has taken place, and left 
at rest, when after twelve to twenty-four hours the taurin will 
separate in a crystalline form.f 

11. Acetamid leaves the body rapidly and unchanged.:!: 

12. Amygdalin cannot be found again with certainty, but the 
urine, according to Lehmann and Ranke, contains considerable 
quantities of formic acid. 

13. Salicin is decomposed as if by oxidizing agents. The 
urine contains salicylic hydride, salicylic acid, and saligenin, 
but no sugar and no phenylic acid. 

14 Santonin. After -yising santonin the urine resembles one 
containing biliary coloring matter. A characteristic is that the 
yellow or greenish color of the urine becomes a cherry red or 
purple red after the addition of potassic hydrate. The color 
does not disappear on boiling, but it does on the addition of 
acids, and is restored again by alkalies. According to Mialhe 
this coloring matter appears to be a product of oxidation, since 
santonin on boiling with nitric acid gives a solution which ex- 
hibits a green color after dilution with water, and which changes 
to an orange red after the addition of potassic hydrate. § 

15. Strychnia, according to O. Schultzen, and morphia, ac- 
cording to the experiments of Bouchardat and Dragendorff, 11 
even in large amounts, pass into the urine. 

16. Yeratria, according to Masing,1[ passes into the urine in 
considerable amount. 



^ Berichte der deutscli. cliem. GesellscLaft, Band 6, p. 1191. 
f Salkowskl, Virchow's Archiv, Band 58, p. 4(30-509. 
\ 0. ScTiultzen and Nencki, loc. cit. 
§ Natta und Smith. Zeitsclirif t f . analyt. Cliem. , Band 4, p. 494, und Band 
10," p. 254. 

II Phami. Zeitsclirif t f. Russland, 1868, Heft 4. 
1 Zeitsclirif t f. analyt. Chem., Band 8, p. 240. 



ACCIDENTAL CONSTITUENTS OF UBINE. 209 

17. Asparagin (amidosuccinamic acid) does not pass into the 
urine unchanged. It decomposes in the economy into succinic 
acid and ammonia, both of which appear in the urine. (Hilger.) 

At the same time, after taking asparagin, as well as asparagic 
acid, the amount of urea is increased in the urine. (Yon Knie- 
riem.) 

18. Indol after its subcutaneous injection becomes converted 
into indican, and appears as such in the urine. (Jaffe, Nencki, 
and Masson.) 

Oxindol and dioxindol become changed into red coloring 
matters, which resemble those obtained by the oxidation of 
aqueous solutions of oxindol and dioxindol in the air. (Nencki 
and Masson.) See page 69. 

19. After taking isatin the urine contains a coloring matter 
which in all of its properties corresponds with indigo red (urrho- 
din). (E. Niggeler.) 

To detect alkaloids in the urine the same methods are to be 
used which are employed in legal cases to separate these sub- 
stances.* 

E. Coloring and Odorous Matters. Most coloring and odor- 
ous matters pass into the urine unchanged or but slightly 
modified. Wohler found in the urine the pigments of indigo, 
madder, gamboge, rhubarb, logwood, turnips, and bilberries, 
besides the odorous matters of the valerian, garlic, assafoetida, 
castor, saffron, and turpentine. On the contrary, he did not find 
camphor, resins, empyreumatic oils, musk, ether, cochineal, 
litmus, sap-green, and alkanet coloring matter. 

On the other hand, according to investigations of E. Nigge- 
ler,t indigo blue passed through the intestinal canal unchanged 
and caused no increase of the indican in the urine. 

* Fresenius, Qualitative Analyse, 13^6 Aufi. , p. 458. 
f Jahresbericht f . Thiercliemie, Band 4, p. 220. 

14 



DIVISION SECOND. 

QUANTITATIVE ESTIMATIONS. 

§ 57. Estimation of the Amount of Urine Secreted in a 
Given Time. 

It must be remembered tbat the determination of the amount 
of urine passed in a given time is tlie basis of all other quanti- 
tative estimations, and should not be neglected in any case. 
Therefore, the amount of the urine, and the time during which 
it was passed, must be annexed to every analysis of urine. 
These determinations can be made either with the balance or 
by measuring, yet only the latter method is now in general use. 

For this purpose the cubic centimeter, one thousand of which 
are equal to one liter (1 liter = 2 pounds, or 1,000 grams of 
water), always serves as the unit of measure. If at the same 
time we know the specific gravity of the urine, the amount of 
which has been determined by measurement, it can be readily 
expressed by weight, since it is only necessary to multiply the 
number of cubic centimeters found by the specific gravity of 
the urine; 1,000 cc. of urine of 1'030 sp. gr., therefore, weigh 
1,030 grams. 

The measurement of the amount of urine should always be 
made in graduated glass cylinders, several of which, small and 
large, should be at hand. 

1. To determine the amount of urine of twenty-four hours a 
measuring vessel which holds at least 2,000 cc. (2 liters), and 
is graduated into 100 cc. divisions, is needed. Such a one may 
be easily prepared by accurately weighing into a preserve jar 
of the proper size 100 grams of water, and carefully marking 
the position of the fluid with a file or diamond; then 100 
grams of water are again weighed into it and the point marked 

210 



QUANTITATIVE ESTIMATIONS. 



211 



Fig. 8. 



again; tliis process is continued until tlie whole glass is grad- 
uated up to 2,000 or 3,000. This vessel can be used directly 
for collecting the urine in twenty-four hours ; it must be care- 
fully covered with a glass plate, however, on which a thin layer 
of tallow, or, better still, wax, has been spread, and kept in a 
cool place, so that there shall be no evaporation of water in the 
first place, and in the second, that the decomposition of the 
urine shall not be hastened by heat. With these vessels it is 
necessary to judge of the amount between each 100 cc, so that 
an error of 10 to 20 cc. may occur ; if we wish to avoid this, the 
urine must be collected in another vessel, and then the measur- 
ing glass filled exactly to a file-mark, and the rest measured 
off in a smaller graduated cylinder. 

2. To determine the amount of urine secreted 
during a short but definite time, finely gradu- 
ated cylinders with a foot are better; such a 
one holds 200 to 300 cc, and must be divided 
into single cubic centimeters. (Fig. 8.) They 
serve for determining the amount of urine for 
each hour very accurately. 

According to the object of the examination, 
sometimes the first, and sometimes the second 
determination is made ; and it is to be remarked 
that the collection of twenty-four hours is better suited to ob- 
serve large, long-continued differences in the secretion of urine, 
and is, therefore, used in most investigations of disease. The 
determination of the amount of urine passed in a short time, 
however, allows transient differences in the secretion to be ob- 
served, and is, therefore, better adapted for studying the action 
of transient influences on the urinary secretion. 

Lastly, we must mention that the urine must be collected 
and analyzed several days in succession in all examinations in 
which it is desirable to obtain an average value, and the mean 
of the results thus obtained must be taken. 




§ 58. Specific Geavity. 

1. By the Arceometer (Urinometer). Although only approxi- 
mate results can be obtained for the true specific gravity of a 
urine by means of an araeometer, yet its use is perfectly legiti- 



212 



ANALT8I8 OF THE UBmE. 



Fig. 9. 



mate for a physician's purposes. Such an araeometer should al- 
low the specific gravity of the urine to be accurately determined 
between 1*000 — the sp. gr. of water — and at least 1*040 — about 
the highest sp. gr. which human urine reaches — even to half a 
degree ; then it ought not to be too large, so that it may serve 
for small amounts of urine also. To obtain the greatest possi- 
ble accuracy with these instruments, it is well to divide the 
specific gravities of 1*000 to 1*040 on two araeometers, so that 
one shall run from 1*000 to 1*020, and the other from 1*020 to 
1*040; the possibility will then be attained of being able to de- 
termine halves and quarters of a degree. 

All instruments of this sort, however, only give correct re- 
sults at a stated temperature for which they are constructed; 
if, therefore, we wish to be very accurate, it is first 
necessary before testing to bring the urine to this tem- 
perature. According to some experiments by Siemon, 
the specific gravity of a urine which at + 12° C. was 
1*021, at +15" C. sank to 1*020, and at +18° C. to 
1*019, so that a difference of temperature of 3° C. cor- 
responds to about a degree of the urinometer. 
Beneke arrived at the same results. 
At my request, Mr. Niemann, of Alfeld (Germany), 
now constructs urinometers which are furnished with 
a small thermometer in the float, on which the normal 
temperature at which the apparatus is constructed is 
designated by a red line. The scale on these uri- 
nometers is considerably longer than those made by 
Greiner of Berlin (Germany). The single degrees are 
large, distinct, and marked with black marks, while 
the half degrees are marked quite distinctly with red 
lines, so that an accurate reading is very much facili- 
tated. I have had for some time two such urinome- 
ters in use and am pleased in every respect with them, 
and therefore recommend them to those who are en- 
gaged in urinary analysis. (Fig. 9.) 

To determine the specific gravity with an araeometer, 
a suitable upright cylinder is four-fifths filled with the 
clear filtered urine, all bubbles of air are removed with 
a glass rod, or better with blotting paper, and the clean 
instrument is then slowly introduced into it. The cylinder 



1,020 



L02S- 



IfiZS 



JMO 



i 




QTJANTITATIVE ESTIMATIONS. 



213 



must necessarily be oi such a width that the urinometer can 
freely float in the fluid and not touch the sides of the glass at 
any point. The reading is accomplished most accurately when 
the eye is brought to a level with the lower part of the 
surface of the fluid, and this is accomplished w^hen the pos- 
terior edge of the surface of the fluid can no longer be seen ; 
the point at which the plane of the fluid cuts the urinometer 
scale is the one which should be read off. When it is not 
rightly held before the eye, either too low or too high, the sur- 
face of the fluid appears to be in the form of an ellipse. The 
araeometer is then pressed a few degrees deeper into the 
urine, allowed to come to rest, and then read off a second 
time as a correction. Carried out in this way, the results 
with a good araeometer, such as Niemann furnishes, are very 
accurate. The araeometers of Greiner, of Berlin, have too short 
scales. 

2. With the Mohr- Westphal Balance, This ingenious and ac- 
curate instrument for determining the speciflc gravity depends 
on the principle that the loss of weight which the same body 
suffers in different 
fluids is proportional 
to the specific gravity 
of the fluid. On one 
arm of the balance, ^9;. 
10, the glass sinker A, 
which has the form of 
a small thermometer, 
hangs by means of a 
fine platinum wire, and 
is exactly equipoised 
by the other arm of the 
balance. The arm of 
the balance, on which 
the glass sinker A 
hangs, is divided into 
ten equal parts. B, C, 
D, and E represent the forms of the weigths, made of brass and 
aluminium, which belong to it. The weights B and C each 
weigh exactly as much as the loss of weight v, which the glass 
sinker A suffers in water, while D is exactly one-tenth of this 



Fig. 10. 




214 ANALYSIS OF THE URmE. 

loss of weight, and the weight E made of aluminium weighs ex- 
actly one one-thousandth of v. 

If the specific gravity of the urine is to be determined with 
this balance, the glass cylinder G, in which the sinker hangs, 
is filled with it. The weights are then so placed that the lever 
stands perfectly horizontal, when the sinker is wholly immersed ; 
this is readily determined by the two points at F. 

For example, if the weight B must be hung on the division 
10 of the lever, the weight D, which is ten times lighter on the 
division 2, and the aluminium weight E, which is one hundred 
times lighter on the division 5 in order to restore the equipoise, 
the specific gravity of the urine is 1*025. 

The mechanician Westphal in Celle (Hanover, Germany) fur- 
nishes these balances of most excellent workmanship at very 
moderate prices. 

3. With the Picnometer. This method is grounded on the fact 
that the specific gravity of a fluid is obtained by dividing the 
absolute weight of a given volume of the fluid examined by the 
absolute weight of an exactly equal volume of distilled water. 
For this purpose a glass with as thin walls as possible, closed 
with a ground-glass stopper, carefully cleaned and dried, and 
holding 40 or 50 cc, is weighed on a fine chemical balance, first 
while empty, and its weight noted. It is then filled perfectly 
full with distilled water and all of the air bubbles are carefully 
removed, the stopper is put in air-tight, and if no bubbles are 
seen, the flask is carefully dried on the outside, first with a linen 
cloth and then with blotting paper, and it is again weighed. 
If the weight of the empty glass already known is subtracted 
from this weight, the exact absolute weight of the volume of 
distilled water which the glass can contain is obtained. The 
weight of this amount of water as well as the temperature at 
which it was obtained is noted once for all. 

If it is desired to ascertain the specific gravity of a urine, the 
empty glass is repeatedly rinsed out with it and then filled with 
the urine, observing the above precautions, closed, carefully 
dried as mentioned above, and the weight determined; from 
this gross weight that of the empty flask is subtracted, and the 
absolute weight of the urine is thus obtained, which corre- 
sponds exactly to the volume of distilled water found in the first 
experiment. From these data the specific gravity of the urine 



QUANTITATIVE ESTIMATIONS. 



215 



is readily reckoned, since it is only necessary to divide its ab- 
solute weight by tliat of the distilled water already known, in 
order to obtain as a quotient the specific gravity of the urine in 
question. 
An example may serve to explain this : 



The flask with distilled water weighs 80 
The flask alone '' 30 



grams. 



It therefore holds 

The flask with urine weighs 

The flask alone '' 



50 

81-2 
30-0 



of water. 



It contains, therefore, 51*2 " of urine. 
The specific gravity of the water — 1*000. 
We then have the proportion : 
50 :51*2— I'OOO (sp. gr. of water) \x (sp. gr. of the urine). 
51-2 X 1-000 



50 



1-024. 



Instead of an ordinary flask it is better 
to use the picnometers made for this pur- 
pose (fig. 11), which have many advantages. 
These glasses are easy to weigh, they hold a 
tolerably large amount of fluid, and obviate 
the shutting in of air bubbles, since the 
latter can escape through the fine capillary 
tube in the ground tube-stopper a. Per- 
fectly complete picnometers have a small 
thermometer in this tube, by means of 
which the temperature may be determined 
at the same time. The calculation is just 
the same as above ; the weight of the dis- 
tilled water which the picnometer can hold 
is determined once for all. 




216 



AJVALTSIS OF THE UMUSTE. 



§ 59. Estimation of the Watek and of the Total Solids 

IN Solution. 

In the estimation of the solid residue of urine many difficul- 
ties stand in the way, which are caused in the first place by the 
readiness with which the urine decomposes, and secondly by 
the very hygroscopic character of the residue. According as 
greater or less accuracy is required, sometimes the first and 
sometimes the second method is chosen. 

1. Ten to fifteen grams or cc. of urine are weighed or mea- 
sured into a rather small accurately- 
weighed porcelain crucible (fig. 12), 
which can be Fig. 13. 

closed with a 
cover, and eva- 
porated to dry- 



FiG. 12. 





ness over the 
water bath. 
Instead of a 

crucible a small glass cup with a ground edge Avliich can be 
hermetically sealed by means of a ground-glass plate (fig. 13) 
may be used. Naturally the residue cannot be ignited in this 
vesseL (§ 60.) 

A water bath adapted to all of these purposes is shown in 
fioure 14. It is made of strong sheet copper, and when in use 
is half filled with water, which is kept at 
the boiling point by means of a small spirit 
lamp. It is furnished with rings of differ- 
ent sizes for evaporating dishes and cruci- 
bles of various diameters ; these rings are 
simply laid on the top. The diameter from a to h is from four 
to six inches. 

The residue thus obtained is not yet entirely freed from water, 
and must, therefore, be dried a still longer time at 100^ C. The 
air bath, figured in the adjoining cut (fig. 15), will serve for 
this purpose. The crucible containing the evaporated residue 
is placed in the wire frame e, and the apparatus heated with a 
small spirit lamp placed underneath. By means of a ther- 
mometer d, fastened in with a stopper at the hole c, the 




QUANTITATIVE ESTIMATIONS. 



217 



temperature is determined, and can easily be kept constant with 
very slight variations. 

After the urinary residue 
has been dried in this man- 
ner one or two hours, the 
crucible is covered and al- 
lowed to cool in a desiccator 
over concentrated sulphuric 
acid, since its contents would 
attract water again from the 
air with great eagerness; 
fig. 16 represents such an 
apparatus, in which 6 is a 
holder made of lead wire on 
which the crucible is placed. 
The vessel is hermetically 
sealed by a glass plate smear- 
ed with tallow. The crucible 




Fig. 16. 



IS carried to the scales in this 
apparatus and weighed quickly. It is now 
for a second time exposed for a while to a 
temperature of 100° C. and weighed again; 
if it has not considerably decreased in 
weight, the operation is finished, and after 
subtracting the weight of the crucible the 
amount of residue is obtained, and is reck- 
oned for the whole quantity of urine. 

If, further, the weight of the residue is 
subtracted from that of the quantity of urine 
taken, the remainder is the amount of water evaporated. 
Example: 




I. Amount of urine in twenty-four hours = 1,000 cc. of a sp. gr. 
1*025. Ten cc.'were evaporated to dryness and the residue dried at 
100° c. 

Crucible with the residue = 24*891 grams. 
Crucible alone = 24*350 '' 



Residue 



0*541 



0*541 grams of residue is contained in 10 cc. of urine, so that in 
1,000 cc. of urine there are 54*1 grams. 



218 



ANALYSIS OF TEE URINE. 



II. 1,000 cc. of urine of 1-024 sp. gr. = 1024-0 grams. 
Of this the residue = 54*1 ^' 



Evaporated water = 969-9 '\ 

2. Even when carried out with the greatest care, this method 
described under 1 gives inaccurate results, since during the 
evaporation and drying the acid phosphate of sodium has a 
destructive action on the urea and decomposes it partially into 
carbonic acid and ammonia. The latter combines with the acid 
phosphate of sodium to form ammonio-sodic phosphate, a com- 
pound which is again decomposed at 100^ C. with the evolution 
of ammonia. As long as the evaporation and drying is con- 
tinued, therefore, an uninterrupted evolution of ammonia is 
observed, which proceeds from the decomposed urea, while the 
residue always retains its acid reaction. If the evaporation 
and drying is carried on in an apparatus in which the ammonia 





■IIIIIIM 




which is set free can be collected and estimated, a satisfactory 
result is at once obtained, if the ammonia is reckoned as 
urea, from the decomposition of which it has without doubt 
arisen, and this amount is added to the residue found on weigh- 



' QUANTITATIVE ESTIMATIONS. 219 

ing. Very satisfactory results may be obtained with the ap- 
paratus (fig. 17) constructed by me, which allows of the collec- 
tion and estimation of the disengaged ammonia. 

A is a water bath twelve centimeters high and eleven centi- 
meters broad, with a tin tube of two and a half or three centi- 
meters in diameter passing through its centre. A glass tube, 
BB, of the shape represented in the figure, can be readily 
pushed through this tin tube, and the porcelain dish seven or 
eight centimeters long and one and j\ broad, for holding the 
urine, is placed inside. The glass tube, BB, is connected at one 
end with the chloride of calcium tube, F, by means of a cork, 
while the portion drawn out and bent is connected by means of 
a doubly perforated cork with the little flask D, in which stan- 
dard sulphuric acid is placed. The drawn-out arm of the tube 
BB reaches nearly to the bottom of the flask. The flask D is 
connected with the aspirator E through the second perforation 
of the cork. 

The estimation is now readily made. The porcelain dish is 
first about three-quarters filled with not too small glass splin- 
ters, it is dried at 100^ C, and then accurately weighed in a 
glass tube which can be closed with a cork covered with tin 
foil. Then exactly two cc. of urine are allowed to run from a 
pipette, which best holds just this amount, on to the pieces of 
glass in the porcelain dish, and it is carefully pushed into the 
tube BB, which is already connected with the little flask D, in 
which there are ten cc. of standard sulphuric acid, and the lat- 
ter is connected with the aspirator. Then the glass tube is 
carefully pushed through the tin tube of the water bath, and 
the second opening is closed with the chloride of calcium tube 
F, by holding the glass tube firmly with the left hand and 
tightly securing the cork in with the right. When the water in A 
is heated to boiling, the cock of the aspirator is opened, having 
first found that the apparatus is air-tight, and the water allowed 
to flow out in such quantity that the air dried in F shall pass 
through the sulphuric acid in D in bubbles which follow each 
other every second. The urine is evaporated in this manner at 
100"" C. in a stream of dry air. In three-quarters of an hour 
this operation is finished, but the residue of the urine persis- 
tently retains the water, and must, therefore, be kept at the same 
temperature for some time longer. If illuminating gas is at the 



220 AliALrSIS OF THE URmE. 

disposal of the experimenter, a stream of dry gas many suitably 
replace the stream of air, and may finally be conducted to the 
lamp under A and burned. The aspirator is thus rendered su- 
perfluous. The pieces of glass facilitate exsiccation very much, 
so that in about three hours the entire operation may be re- 
garded as completed. The gas or air stream is now inter- 
rupted, the chloride of calcium tube removed, the tube re- 
moved from the water bath, and the little porcelain dish 
introduced into the tube in which it was weighed before the 
evaporation, which tube is then immediately tightly closed with 
the cork. After complete cooling in the desiccator the tube is 
weighed ; the increase of weight gives the amount of urinary 
residue found in two cc. of urine. Next the ammonia evolved 
must be estimated. First the carbonate of ammonium which 
is usually found sublimed in the evaporating tube is washed 
into the flask, then the cork is removed, and the bent arm is 
also washed with water from a wash bottle, one or two drops of 
tincture of litmus or cyanine solution are added, the fluid is 
heated to boiling to drive out all carbonic acid, and the unsatu- 
rated acid titrated with sodic hydrate. It is well to calculate 
the sodic hydrate immediately as urea ; the number of cc. now 
used, less than the number required to saturate the original 
acid, directly gives the amount of urea decomposed, which 
added to the weighed residue yields the whole amount of solid 
constituents of the urine. 

The standard sulphuric acid used in this estimation should 
contain 2*667 grams of sulphuric acid in the liter, so that 1 cc. 
of it shall be saturated by 0*0011335 grams of ammonia, cor- 
responding to 0*002 gram of urea. If, then, to such sulphuric 
acid sodic hydrate is added of such a strength that 1 cc. of the 
former requires just 2 cc. of the latter for its exact saturation, 
each cc. of the sodic hydrate, less than 20, required to saturate 
the 10 cc. of sulphuric acid, exactly corresponds to 1 milligram 
of urea. 

Example : 

Two cc. of urine yielded 0*10 grams of solid residue in the little 
dish. The ten cc. of sulphuric acid required sixteen cc. of sodic 
hydrate after the experiment was ended ; there were, therefore, four 
cc. neutralized by the ammonia evolved, and these correspond to 



QUANTITATIVE ESTIMATIONS, 221 

0-004 grams of urea. Two cc. of urine then contained 0*104 grams 
of residue, and one thousand parts 52*0 grams. 

3. The whole amount of the solid constituents of the urine 
can be approximately reckoned from the specific gravity when 
determined with accuracy and with exact observation of the 
temperature. This is a fact which I have convinced myself of 
by a series of determinations. (See Analytical Experiments.) 
If the three last figures of the specific gravity carried out to 
four decimals is multiplied by the number 0*233, the product 
gives approximately the amount of solid matters in 1,000 cc. of 
urine. 

Example : 

The amount of urine in twenty-four hours =1*500 cc. 
The specific gravity " '' =1-0134 

The amount of solid matters in 1,000 cc. =(0-233 x 134) =31 -22 
grams. The amount in 1,500 cc. therefore = 46*83 grams, while by 
weighing, according to method 2, 46*59 were found. 

The table given in the analytical appendix shows bow large 
the error may be in this method. 

§ 60. Estimation of the Non-Yolatile Salts. 

To determine the total non-volatile salts contained in the 
urine, a measured quantity of urine is evajDorated to dryness 
and ignited until all of the carbon is consumed. Yet this sim- 
ple method is subject to several sources of error, for at too 
high a temperature some of the chlorides present volatilize, 
and at a red heat the separated carbon may reduce the sulphates 
and phosphates, changing the former into sulphides and de- 
veloping phosphorus fumes from the latter. Besides, complete 
ignition of the charcoal requires a long time, since enclosed by 
the large amount of chlorides which are readily fusible, it is 
protected from contact with the air. All of the above sources 
of error may be reduced to a minimum by the following method 
when carried out with care. 

Ten cc. of urine first filtered are placed in a small weighed 
platinum dish with a well-fitting cover and evaporated to dry- 
ness on the water bath. The dish is then placed on a platinum 



222 AWALYSIS OF THE URINE. 

triangle and carefully heated with as little fire as possible until 
the organic matters are carbonized, and no more gas is evolved 
from the swollen mass. After cooling, the contents of the dish 
are covered with boiling water, it is allowed to stand a short 
time, and the colorless feebly alkaline fluid is filtered through 
the smallest possible filter, the weight of whose ash is known. 
The carbonized residue is freed from all soluble salts by re- 
peatedly washing it with hot water, the filter is then washed 
and finally dried in the same platinum dish on a water bath. 
The platinum dish and its contents are then heated to a low 
red heat, and the carbonized residue and the filter are thus 
easily and completely consumed. The platinum dish, when the 
residue is free from all carbon, is put back on the water bath, 
the fluid obtained by extracting the first carbon residue is added 
and evaporated to dryness. The salts obtained are last of 
all heated to a low red heat before weighing, but the saline 
residue must first be dried a long time, since otherwise a loss 
may readily occur by decrepitation. For the same reason the 
dish must be kept well covered during the ignition and the 
temperature only raised to a dull red in order that no chlorides 
shall volatilize. 

If the dish is finally cooled over sulphuric acid, weighed, and 
the weight of the dish and filter ash subtracted from the gross 
weight, the remainder is the total amount of the non-volatile 
salts contained in ten cc. of urine. 

Example : 

The amount of urine = 1,500 cc. 

The platinum dish with cover and ash of 10 cc. = 14*243 grams. 
The platinum dish alone = 14-120 '^ 



0-123 
Filter ash = 0-001 



a 



Non-volatile salts in 10 cc. of urine = 0*122 
10 : 0*122 = 1,500 : x. x = 18*3 grams. 

§ 61. Estimation of the Coloeing Matters. 

A. TJie Color Table. (See Plate lY.) 

Vogel has succeeded by a large number of observations in 
establishing the color scales, given below, for the different 



QUANTITATIVE ESTIMATIONS. 

shades of healthy and pathological urine. These he has imi- 
tated artificially by mixing different amounts of gamboge, car- 
mine lake, and Prussian blue. He distinguishes three groups 
or shades. 

/. Group, Yellow Urines. 

The color is a yellow (gamboge) more or less diluted with 
water. The group has three shades of color whose starting 
point is the rarely occurring colorless urine. 

1. Pale yellow (gamboge with much water). 

2. Light yellow (gamboge with little water). 

3. Yellow (gamboge with very little water). 

11. Group. Beddish Urines. 

Eed is more or less mingled with yellow (gamboge with car- 
mine lake). The urines of this group are designated by the 
adjective "high-colored." Three shades of color belong here 
also : 

4 Eeddish yellow. A little red is mingled with the yellow, 
but the latter is more prominent. (Gamboge with a little car- 
mine lake.) 

5. Yellowish red. The red color together with the yellow is 
more distinct. (Gamboge with a little more carmine lake.) 

6. Red. The red predominates, yet there is still some yellow 
mixed with it. (Carmine lake with a little gamboge.) 

III. Group. Brown (darF) Urines. 

The red color passes through brown almost into black. 
(Gamboge and carmine lake with more or less Prussian blue.) 

7. Brown red. A little brown is mingled with the red. 

8. Eed brown. More brown than the above. 

9. Brownish black. Almost black, yet with a tinge of brown- 
ish red. 

The practised eye can still distinguish intermediate shades 
between these, when it can be said : the color is between light 
yellow and yellow ; it approaches nearer to the reddish yellow 
than the yellowish red, etc., but according to Yogel these nine 
shades suffice. 

B. Value of these Color Scales. The shades of color correspond 
to certain relative amounts of coloring matter. It has been 



224 



ANALYSIS OF THE URmE. 



found that by diluting a higher number with water all the lower 
numbers can be produced. All nine "shades of color are in the 
same series, so that the color of urines may be regarded as dif- 
ferent dilutions of one and the same coloring matter. But we 
must naturall}^ leave out of question the accidental colors, which 
rarely occur, due to the presence of bile, medicinal or food 
pigments, etc. These experiments carried out quantitatively 
prove that a urine diluted with an equal volume of water pro- 
duces nearly the next lower shade : 200 cc. of urine of a yellow- 
ish-red color diluted with 200 cc. of water becomes reddish 
yellow, and so forth. These relations are about the same for all 
parts of the scale, from which it follows that they may serve to 
determine the relative amount of coloring matter in different 
urines. 

The following table serves for such quantitative estimations : 



I. 


II. 


III. 


IV. 


V. 


VI. 


VII. 


VIII. 


IX. 




1 


2 


4 


8 


16 


32 


64 


128 


256 


pale yellow = I. 




1 


2 


4 


8 


16 


32 


64 


128 


light yellow = 11. 






1 


2 


4 


8 


16 


33 


64 


vellow := III. 








1 


2 


4 


8 


16 


32 


reddish yellow = IV. 










1 


2 


4 


8 


16 


yellowis i red = V. 












1 


2 

1 


4 
2 
1 


8 
4 
2 
1 


red = VI. 
brownish red — VII. 
reddish brown = VIII. 
brownish black — IX. 



C. Application of the 3IetJiod. This table which has been 
drawn up serves us for the quantitative comparison of the 
amounts of urinary coloring matter eliminated ; it shows how 
much coloring matter equal parts of urine of different colors 
contain relatively. If a certain volume of pale-yellow urine 
contains one part of coloring matter, the same volume of yel- 
lowish red contains sixteen parts, of red thirty-two parts, of 
brownish black two hundred and fifty-six parts, etc. It further 
shows that one volume of yellow urine contains just as much 
coloring matter as four volumes of pale yellow, one volume of 
red as much as four volumes of reddish yellow, or thirty-two 
volumes of pale yellow, etc. If, therefore, one person passes 
1,000 cc. of yellow urine in twenty-four hours, and another in 
the same time 4,000 cc. of pale yellow, both secrete an equal 
amount of coloring matter. 

Now, in order to make an approximate comparison by figures 



QUANTITATIVE ESTIMATIONS. 225 

possible, Vogel places the quantity of coloring matter which 
1,000 cc. of pale yellow urine contains — 1. 

But in order to obtain harmonious results by comparing the 
color of the urine with the color table, the urine must in the 
first place be perfectly clear ; in most cases, therefore, it must 
be filtered, and in the second place it must be examined by 
transmitted light in a layer four or five inches thick. There- 
fore, glasses four or five inches in diameter are used which can 
hold 800 or 1,000 cc, since the color in thinner layers will ap- 
pear too light when compared with the table. 

Example : 

1,800 cc. of urine having a yellow color are passed. 

1,000 cc. pale yellow — 1 part coloring matter ; but yellow, ac- 
cording to the table, contains four times as much ; therefore, we 
have the following proportion : 

1,000 :4 = 1,800 :x = 1'^ as the amount of coloring matter in 
1,800 cc. of yellow urine, the coloring matter in 1,000 cc. of pale 
yellow urine being considered as the unit. 

QUANTITATIVE ESTIMATIONS OF INDIVIDUAL SUBSTANCES. 

§ 62. YoLUMETRic Analysis. 

The use of this method renders urinary analysis simpler and 
its performance more rapid. In determining the weight of a 
body by titration, we do not do it by weighing the compound 
precipitated by any reagent, but we ascertain the amount of 
the solution of a reagent necessary to complete a certain re- 
action, and from this reckon the quantity of the material which 
was present. These determinations, which are always carried 
out by measuring the solution of the reagent used, are success- 
ful, however, only under certain conditions, on which alone 
their accuracy depends ; these are the following : 

1. The strength of the solution of the reagent must be most 
accurately known, and the amount of the standard solutions 
used must be capable of exact determination. 

2. The end of the reaction, that is, the point at which just 
enough of the standard solution has been added, must be recog- 
nized in a distinct and striking manner. 

3. The decomposition, on the accomplishment of which the 
analysis depends, must always remain the same. 

15 



226 



ANALYSIS OF TEE URINE. 



4 The decomposition must be so managed that none of the 
active or reactive agent is lost. 

General rules for attaining these conditions cannot be given 
well, since they differ with each substance, and must be treated 
more in detail in speaking of each one separately. Yet, before 
I pass to the individual methods, it is necessary to speak of the 
apparatus required, as well as generalities in their execution. 



15CC 



10 cc 



§ 63. I. Appakatus. 

On account of the superiority of the French system of weights 
Fig. 18. ^^^ measures, these only are employed in quan- 

titative chemical determinations. It is well 
known that there is here an intimate connec- 
tion between volume and weight, so that 1,000 
cc. of water at its greatest density, that is, at 
+ 4° C, = 1 liter, which weighs exactly one kil- 
ogram or 1,000 grams ; a cubic centimeter, there- 
fore, corresponds exactly to one gram. 

The measuring vessels in which volumetric 
analyses are performed are all divided into 
cubic centimeters (cc.) ; of these may be men- 
tioned : 

1. The Graduated Pipette. This is the glass 
apparatus whose form is shown in fig. 18, a and 
I) ; it is used in measuring off the necessary 
fluids, and, therefore, has a mark on its neck 
up to which it contains just 50, 20, 15, 10, 4, 
3, and 2 cc. In measuring, the end of the 
pipette is dipped into the fluid, which is sucked 
up until it has risen above the mark in the neck ; 
the opening above is then closed by the finger 
slightly moistened (neither wholly dry nor yet 
JL wet), the pipette is freed from fluid adhering to 
the outside by wiping, and the solution is allowed 
to flow from the pipette by slightly lifting the 
finger, until it stands exactly at a level with the 
mark ; this point is determined by holding the 
surface of the fluid on a level with the eye. 
Having reached this point the pipette is tightly closed with the 



QUANTITATIVE ESTIMATIONS. 



227 



^z 



^s 






Fig. 20. 



finger again, and the contents may be allowed to flow into any 
vessel at pleasure. It must be observed, however, how the 
pipette has been graduated, whether the last drop, which col- 
lects at the lower end after a time and which may be removed 
by blowing it out, must be taken or not. The most accurate 
and most suitable are the "pipettes a I'ecoulement," which are 
so graduated that they allow the designated amount of fluid 
to flow out directly in a stream, so that the drop which remains 
adherent to the lower end need not be blown out. It is pre- 
FiG 19 f^^s-ble in all cases to place the point of the pipette 
1^;^ on the moistened side of the glass, while it is being- 
emptied. This method of measuring gives the most 
constant results; it is self-evident, however, that the 
pipettes must be graduated according to this method 
of reading ojff. For 
urinary analysis pi- 
pettes of 50, 30, 20, 
15, 10, 3, and 2 cc. are 
necessary for a com- 
plete outfit. 

The following ap- 
paratus serves for 
measuring standard 
solutions. 

2. Mohrs Pipette. 
These pipettes are 
graduated through- 
out their entire 
length, and hold 30 
or 40 cc, each of 
which is again di- 
vided into ten parts 
(that is, into yV cc). 
(Fig. 19.) They are 
not drawn out at 
the top, so that 
fluids may be easily 
poured into them, and the opening may then be closed with a 
cork. The following very simple contrivance, and one which 
at the same time answers all requirements, allows the standard 




Fig. 21. 




228 



AJVALTSIS OF THE URmE. 



solutions to flow out drop by drop. A short piece of vulcanized 
rubber tubing, fig. 20, aa, which is pressed together by a wire 
clamp hh, fig. 21, by which it is hermetically closed, but can be 
more or less opened by pressure applied to the two plates c, c, 
has a small glass tube, d, ending in a fine point, introduced into 
its lower end. This rubber tube is drawn over the small end, 
by of the pipette, represented in ^^. 19, which is then fastened 
in a wooden stand so that it is perfectly vertical. Fig. 22 
shows the entire apparatus. When ready for use the pipette 
is filled to the 0-point with the standard solution, the urine to 
be tested is measured off, and the standard solution is allowed 
to flow, at last drop by drop, 
by opening the wire clamp 
until the right point is ex- 
actly reached. By means 
of this ingenious contriv- 
ance we not only obtain a 

Fig. 23. 



Fig. 23. 




more rapid flow, but also a surer discharge of the single drops. 
In a series of investigations which extend over a long time it 
is well to have two or more such pipettes on a stand, so that 



QUANTITATIVE ESTIMATIONS. 



229 



tliey may be left standing wholly or partly filled, if the upper 
opening is closed with a stopper, without danger of evapora- 
tion. 

Fig. 23 shows a similar arrangement which might be very 
useful to physicians, and is sufficiently intelligible without an 
explanation, ah, on which the eight arms are fastened, is a 
brass case which rests on a clamp, and which can be readily 
turned on its axis. The pipettes are held above by a screw 
clamp, while below they simply rest on the holder, which is 
turned out conically and has a hinge, so that the pipettes can 
be readily taken out. c, c, c are pieces of cardboard which are 
fastened by a small clamp to each arm, and on which the nature 
of the fluid in the pipette is recorded. Finally, (i is a level 
resting on four screws to keep the whole apparatus perpendicu- 
lar. It is self-evident that by constructing the apparatus some- 
what larger six or eight pipettes maybe held by it. 

The same purpose is served by 

3. The Graduated Burette. The ordinary form of this ingeni- 
ous apparatus is pictured in fig. 24 The narrow Ym. 24. 
tube serves for pouring the fluid out, and must, 
therefore, be placed somewhat lower than the open- 
ing of the broad tube, so that the fluid can be con- 
veniently removed. These burettes either hold 
30 cc. and are then divided into tenths like the 
pipettes in fig. 19, or they contain 50 cc. and are 
then divided into 100 degrees, each one of which 
marks half a cc. When used they are filled to 
above the 0-point with the standard solution, and 
then the excess is poured out of the narrow tube 
exactly to the 0. Mohr's apparatus described above 
renders these easily perishable instruments rather 
superfluous. The Mohr pipette and the burette 
must each be graduated a Vecoiilemenf. 

4. The Graduated Cylinder. This is used for pre- 
paring the standard solutions, and is represented 
in fig. 25. Such a cylinder must contain 500 or 
600 cc. and have a division line for every 5 cc. The 
so-called measuring flasks serve the same purpose, 
fig. 26 ; they are filled to a mark in the neck, and 
hold exactly one, one-half, or one-quarter of a liter. 



I 



10 






30 



40 



These 



230 



ANALYSIS OF THE URINE. 



flasks are preferable to tlie cylinder in the preparation of stan- 
dard solutions.* 



§ 64. II. Perfoemance. 

In carrying out the volumetric method, as already remarked 
above, we must pay the greatest attention to the necessary 
standard solutions, since the correctness of the results ob- 
tained depends solely on the accuracy of these. Special direc- 
tions will be given with each method, and we must remark at 
the same time, that such normal solutions must always be only 
prepared and used at medium temperatures, since their volume 
would be considerably changed by heat. Furthermore, certain 




Fig. 26. 



Fig. 25. precautions are 

to be observed 
in reading off 
the level of the 
fluid in the gra- 
duates, which 
precautions 
must be accu- 
rately followed 
in carrying out 
the methods : 

1. Care must 
be taken that no 
bubbles render 
the height of the 

fluid uncertain ; they must, therefore, 
be removed either by waiting or by 
being broken up by a glass rod. 

2. The surface of the fluid must be 
level; this is attained in pipettes by allowing them to hang 
freely, but in burettes best when they are placed against a 
window pane. 

3. If any sort of fluid is poured into a narrow tube, it is ob- 
served that its surface forms a curve as the result of capillarity ; 
if this curve is carefully examined, best by transmitted light. 




* The mechanician Niemann, in Alfeld near Hanover, Germany, furnishes the 
above pieces of apparatus of great eycellence and at low prices. 




QUANTITATIVE ESTIMATIONS. 231 

several zones may be readily distinguished in it. (Fig. 27.) 
Now in reading off it is not immaterial Avliether sometimes 
the upper and sometimes the lower edge or the middle of the 
curve coincides with the division line of the tube. The mea- 
surements are made most accurately when the eye is placed on 
a level with the lower edge of the dark zone, fig. 27, after the 
pipette or burette has been brought to the perpendicular, and 
the division line of the tube is read off from this ; pig. 27. 
this edge can be most sharply brought out and ob- 
served by transmitted light. 

If the urine to be tested has been measured in 
this manner, and the pipette or burette has been 
filled with the standard solution, the latter is al- 
lowed to flow into the urine drop by drop until 
the end reaction distinctly appears. If this end re- 
action is very apparent through the whole fluid, it 
shows a great excellence of the method ; but if this 
is not the case, the mixture must be frequently 
tested toward the end of the experiment until the right point 
has been finally reached. Each method, moreover, has its own 
reaction, which must be spoken of separately. If the standard 
solution has been added up to this point, the volume used is 
read off with the observance of the above precautions, and 
the amount of the substance to be determined is reckoned 
from it. 

For example : If, in estimating the amount of urea in 10 cc. of 
urine, 20 cc. of the mercury solution have been used, each cc. of 
which exactly corresponds to 10 milligrams of urea, there are con- 
sequently in those 10 cc. of urine (20 x 10) 200 milligrams of urea ; 
in 1,000 cc. then 20-00 grams. 

Lastly, we must observe, in using a burette {^g. 24) care must 
be taken not to spill the fluid out of the wide tube, by inclin- 
ing it too much. This may readily happen, if a drop remains 
hanging in the narrow delivery tube and hinders the penetra- 
tion of the column of fluid ; this disturbing element, however, 
may be easily removed by blowing into the tube. 

The amount of urea, chlorine, phosphoric acid, free acids, 
sulphuric acid, lime, ammonia, and sugar in the urine may be 
determined volume trically. 



232 AliALYSIS OF THE UJRINE. 

§ 65. Estimation of Urea by Liebio's Method. 

A. Principle, If a dilute solution of mercuric nitrate is added 
to a dilute solution of urea, and if the free acid of the mixture 
is neutralized from time to time with carbonate of sodium, a 
flocculent, bulky, white precipitate is obtained, which is insoluble 
in water. If the solution of mercury and carbonate of sodium 
are added alternately as long as this precipitate is formed, a 
point occurs at which the mixture assumes a yellow color, due 
to the formation of mercuric hydrate or a basic salt from the ad- 
dition of the carbonate of sodium. If now the fluid is filtered, 
it contains no determinable amount of urea ; all of the urea is 
precipitated in combination with mercuric oxide. The precipi- 
tate which takes place contains to one equivalent of urea four 
equivalents of mercuric oxide. The above-mentioned yellow 
color with carbonate of sodium will not begin until a volume 
of the mercuric solution, in which there are seventy-seven 
parts of oxide, has been added to ten parts of urea in the solu- 
tion of urea, that is, four equivalents to one equivalent of urea. 

If no more mercuric solution is added to the solution of urea 
than is necessary for a complete precipitation, the mixture tested 
with carbonate of sodium still remains white ; but if it is now 
allowed to stand a few hours the character of the precipitate 
changes, it becomes crystalline, and the supernatant fluid then 
gives a yellow precipitate with alkalies. In the acid solution 
on long standing the compound with four equivalents of mer- 
curic oxide is reduced to a compound which contains a less 
amount, that is, a part of the mercuric oxide enters into solu- 
tion again. 

In order now to reach the point at which all of the urea is 
precipitated, and to determine whether the necessary amount 
of the mercuric solution has been added to form the compound 
with four equivalents of mercuric oxide, it is necessary to neu- 
tralize with carbonate of sodium. If a drop of the mixture added 
to a drop of a solution of carbonate of sodium in a watch glass 
remains white, free urea is still present in the fluid : if, when 
the two drops flow together, a yellow pellicle appears on 
the surface, the limit is reached, or, more accurately, is a little 
exceeded. To bring out this end reaction, only a very slight 
excess of jnercuric oxide is necessary. 



QUANTITATIVE ESTIMATIOI^S. 233 

If we know the amount of oxide which onr mercuric solution 
contains, and if we further determine the volume which must 
be added to a solution of urea of unknown strength until the 
latter is completely precipitated (until on neutralizing a drop 
of the mixture with carbonate of sodium a yellow color appears), 
the amount of urea in the solution can be reckoned. Or, on the 
other hand, if a certain volume of the mercury solution has 
been required to precipitate a known amount of urea, for ex- 
ample, 100 mgrm., the same volume of the mercury solution 
will indicate the same amount of urea, 100 mgrm., in solutions 
containing unknown amounts. 

B. Preparation of the Necessary Solutions. 

1. Urea Solution of Knoion Strength. Four grams of pure 
urea, dried at 100° C, are dissolved in water and diluted until 
the volume of fluid amounts to exactly 200 cc. 10 cc. of this 
solution contain exactly 200 mgrm. of urea. 

2. Solution of Mercuric Nitrate. The solution of mercury which 
serves to determine the urea in urine must be of such a strength 
that 20 cc. of it just suffice to completely precipitate the urea 
in 10 cc. of solution 1 (in which there are 200 mgrm. of urea). 

1 cc. of the mercury solution should correspond to 10 mgrm. 
of urea, and for this purpose it must in the first place contain a 
quantity of oxide sufficient to form with 200 mgrm. of urea the 
compound with four equivalents of mercuric oxide, and also 
a slight excess which serves to indicate the complete precipita- 
tion of the urea, so that after adding the last drop of the 20 cc. 
to 10 cc. of the solution of urea a distinct yellow color is evi- 
dent, when a few drops of the mixture are treated with carbo- 
nate of sodium on a w^atch glass. 

Liebig has found that to 100 mgrm. of urea, which according 
to the calculation require 720 mgrm. of mercuric oxide, 10 cc. 
of the mercury solution must contain 772 mgrm. of oxide to 
produce in dilute fluids the reaction of mercuric oxide with 
carbonate of sodium distinctly. Each cc. of the solution must, 
therefore, contain an excess of 5 '2 mgrm. of mercuric oxide; 
and a liter 77*2 grm. of oxide in all, or 71*48 grm. of metallic 
mercury. 

a. Preparation from Pure Mercury. 

71*48 grrfe. of chemically pure mercury are weighed off, placed 
in a beaker and dissolved in pure nitric acid. When solution 



234 ANALYSIS OF THE URINE. 

lias resulted, it is warmed and nitric acid frequently added 
until no more traces of nitrous vapors are seen to escape, in 
otlier words, until the mercurous oxide is completely trans- 
formed into mercuric oxide, and it is then evaporated in the 
same vessel to a thick syrup. The mercuric nitrate thus ob- 
tained is then diluted with water to exactly a liter ; if a basic 
salt separates, it is allowed to settle, the clear fluid is carefully 
poured off, and the precipitate is dissolved again by a few drops 
of nitric acid. The accuracy of the solution thus obtained 
must now be tested in the manner described below. 

b. Preparation from Mercuric Oxide. 

It is best to prepare the mercury solution from pure mercuric 
oxide ; it can also be readily prepared in a porcelain dish by 
heating mercurous nitrate, which has been re crystallized several 
times. There occurs in commerce a mercuric oxide sufficiently 
pure for this purpose, for when it leaves no visible residue 
when heated on platinum foil, it is quite suitable. 77*2 grm. of 
such mercuric oxide which has been dried at 100° C. are accu- 
rately weighed, dissolved in as little nitric acid as possible in a 
porcelain dish at a gentle heat, evaporated to a syrupy consis- 
tency and then diluted to one liter. If a basic salt should sep- 
arate, nitric acid is added drop by drop until the precipitate 
just disappears. 

According to Dragendorff, yellow mercuric oxide is precipi- 
tated from a solution of 96*855 grm. of pure corrosive sublimate 
by dilute sodic hydrate ; it is first washed by decantation and 
then on a filter. This precipitate is afterward dissolved in a 
sufficient amount of nitric acid and diluted to nearly a liter. 
The exact strength of the solution is fixed by titrating with the 
normal solution of urea as given under d. 

c. Preparation from Mercurous Nitrate, 

If no chemically pure mercury or mercuric oxide can be 
obtained, crystalline mercurous nitrate must be procured, and 
this converted into mercuric oxide by heating with nitric acid. 

d. To Standardize the Prepared Mercury Solution. 

Exactly 10 cc. of the solution of urea, 1, are measured off 
with a pipette, poured into a small beaker, and then the ap- 
proximately dilute mercury solution is added drop by drop, 
until a few drops of the mixture neutralized with cgwbonate of 
sodium on a watch glass give a distinct yellow color. 



QUANTITATIVE ESTIMATIONS. 235 

If, for example, 19*25 cc. of the mercury solution have been 
required to produce the end reaction, 7*5 cc. of water are added 
to each 192 '5 cc, and thus 200 cc. of solution are obtained, of 
which 20 cc. will exactly precipitate the urea from 10 cc. of the 
urea solution. Its accuracy is confirmed by a second test : if 
the yellow color appears distinctly after adding 20 cc, the solu- 
tion may be used for determining the urea in urine. 

3. Bai^yta Solution. This is obtained by mixing one volume 
of nitrate of barium solution and two volumes of caustic baryta, 
both solutions saturated in the cold. 

C. Performance. 

In order to be able to determine the urea in the urine by this 
method, the phosphoric acid must first be removed. Therefore 
40 cc. of urine are measured off, with a pipette, treated with 20 
cc of the baryta solution, and the precipitate which occurs is 
separated by filtering through a dry filter. For each analysis 
15 cc. of the filtrate are measured off, which, therefore, contain 
exactly 10 cc. of urine. In most cases one volume of the baryta 
solution to two volumes of urine is sulB&cient to remove all of 
the phosphoric and sulphuric acids, so that some baryta still 
remains in the solution. But if the urine contains alkaline car- 
bonates, which under certain circumstances may consist of car- 
bonate of ammonium from the decomposed urea, or if it has 
a very strongly acid reaction, one volume of baryta solution 
to two volumes of urine are often not sufficient ; then more 
must be taken. If three volumes of baryta solution are mixed 
with four volumes of urine, 17*5 cc of the filtrate are taken 
(corresponding to 10 cc of urine) ; with equal volumes of baryta 
solution and urine 20 cc. are taken for the analysis, etc. 

The standard mercury solution is allowed to flow from a 
Mohr pipette into this measured amount of uiine without previ- 
ously neutralizing and with constant stirring, and when no more 
precipitation is observed and the mixture no longer thickens, the 
test is performed. For this purpose a few drops of the mixture 
are placed on a watch glass by means of a glass rod, and a few 
drops of carbonate of sodium solution are allowed to flow on to it 
from the edge of the watch glass ; a Mohr's india-rubber pipette 
is good for this purpose. If the mixture retains its white color 
after some seconds, there is still some free urea present, and a 
few more drops of the mercury solution are added and it is 



236 ANALYSIS OF THE UBINE. 

again tested ; this process is repeated until at a new trial on 
the watch glass a distinct yellow color results after the carbo- 
nate of sodium solution has been added. The shade must natu- 
rally be the same as that at which the mercury solution was 
originally standardized, for by sometimes adding the solution 
until a weak and sometimes until a strong yellow color is pro- 
duced, an error is caused, which with a little experience can be 
avoided. 

The amount of urea is then reckoned from the number of cc. 
of the mercury solution which have been used, but under cer- 
tain circumstances a few corrections are to be made which are 
mentioned below. 

D. Modification of the Process and Corrections Required by Dif- 
ferent Circumstances. 

1. The Urine contains more than 2 per cent, of Urea. 

Our mercury solution is standardized by a urea solution 
which contained 2 per cent, of urea; we need, therefore, for 
the complete precipitation of the urea in 15 cc. of our urea 
solution, and for producing the end reaction with carbonate 
of sodium, 30 cc. of mercury solution. The mixture, therefore, 
will amount to 45 cc, and we have in it 30 x 5 '2 = 156 mgrm. 
of free mercuric oxide ; each cc. contains, therefore, 3*47 mgrm. 
If the 15 cc. of the urea solution contain 4 per cent, of urea, and 
if to 15 cc. of the same 60 cc. of mercury solution are added, 
there are together 75 cc. of mixture, in which there are 60 x 5*2 
= 312 mgrm. of free mercuric oxide, in each cc, therefore, 4*16 
mgrm., and consequently 0*69 mgrm. more oxide than is neces- 
sary to produce the end reaction with carbonate of sodium. 

It has thus happened that in a urinary analysis an error 
is made when the amount of urea is more than 2 per cent., 
so that the true amount of urea is diminished. If the urine 
contains, as in the above case, 4 per cent, of urea, 60 cc. of 
the mercury solution would not be necessary, but only 59*37 cc. 

This error is avoided by adding, when 15 cc. of urine are 
taken, for the number of cc. of mercury solution more than 30 
cc which are used, half this number of cc. of water to the mix- 
ture before testing with carbonate of sodium. If, for example, 
50 cc. of mercuric solution are used to 15 cc. of urine, that is, 
20 cc. more than 30, then 10 cc. of water i;aust be added before 
testing with carbonate of sodium. 



QUANTITATIVE ESTIMATIONS. 237 

2. The Urine contains less than 2 per cent of Urea. 

For the same reasons which are given above, when the urea 
in the urine only amounts to 1 per cent., to obtain the end 
reaction there will be required for 15 cc. of urine, not 15 cc. of 
the mercury solution, but 15 "3 cc. Through this error the 
amount of urea is found to be increased, and in order to obvi- 
ate it when the urine is dilute, for every 5 cc. of the mercury 
solution less than 30 cc. which are used, 0*1 cc. must be sub- 
tracted from the number of the cc. of mercury solution used. 
If to 15 cc. of urine 25 cc. of mercury solution are used, that is, 
5 less than 30 cc, for these 5 cc. 0*1 cc. is subtracted and the 
calculation made for only 24*9 cc. of the mercury solution. 

3. The Urine contains Chloride of Sodium. 

When the amount of chloride of sodium reaches 1 or IJ per 
cent., it exercises an influence on the determination of urea with 
mercuric nitrate. If, for instance, to 10 cc. of our urea solution 
are added 20 cc. of the mercuric solution, a distinct reaction for 
mercury with carbonate of sodium is obtained at the end, but 
this reaction fails when we add 100 to 200 mgrms. of chloride of 
sodium to the solution of urea, and in order to make it appear 
now we must add IJ or 2J cc. more of the mercury solution. 
The determination of the urea comes out 15 or 25 mgrm. too 
high, therefore. The same is the case with the urine also if it 
contains 1 or 1 J per cent, of chloride of sodium. The formation 
of corrosive sublimate is the cause of this. 

Mercuric nitrate and chloride of sodium mutually decompose 
each other, as is well known, into corrosive sublimate and 
nitrate of sodium, but corrosive sublimate does not precipitate 
a feebly acid solution of urea, and therefore remains in solution. 
This is naturally the case also in the determination of urea in 
the urine ; the excess of mercuric oxide which should give the 
yellow color on the addition of carbonate of sodium is not now, 
however, in the form of a nitrate, but of corrosive sublimate to- 
gether with free nitric acid. If we now add carbonate of sodium 
to this mixture bicarbonate of sodium is formed by the free 
nitric acid, and this does not precipitate the corrosive sublimate, 
therefore the reaction does not occur, and we must add some 
more mercuric nitrate in order to obtain it. If the mixture 
contains a larger amount of chloride of sodium than 1 or 1 J per 
cent., the amount of corrosive sublimate formed increases with 



238 ANALYSIS OF THE URINE. 

it, but by the addition of carbonate of sodium the carbonic 
acid which is freed is no longer sufficient to prevent the preci- 
pitation of the mercuric oxide ; there results, therefore, now a 
brownish-yellow precipitate. According to Liebig this is the 
reason why the indication of the complete precipitation of urea 
in the presence of a certain quantity of chloride of sodium (1 or 
1\ per cent.) is deferred, and the limit of the reaction does not 
extend, if the amount of chloride of sodium increases still more. 

If a urine, therefore, contains from 1 to IJ per cent, of chlo- 
ride of sodium, to obtain the right number of milligrams of 
urea in 10 cc. of urine two must be subtracted from the whole 
number of cc. of the mercury solution used, and the remainder 
only reckoned for urea ; the results obtained are then more 
accurate and comparable. 

If it is necessary to know the absolute quantity of urea in 
the urine, the chlorine must first be removed by a solution of 
nitrate of silver, 1 cc. of which exactly corresponds to 10 mgrm. 
of chloride of sodium. 

This solution of silver is obtained by dissolving 29*075 grm. 
of fused nitrate of silver in water and diluting the solution to a 
liter. 1 cc. corresponds to 10 mgrm. of chloride of sodium ; it 
is the same silver solution which is used for determining the 
chlorine according to Mohr's method, § QQ, B, 1. The method 
of performing it is as follows : 

The amount of chloride of sodium in 10 cc. of the original 
urine is determined by means of the silver solution according 
to § QQ>. If, for example, we have used 17*5 cc, the presence of 
175 mgrm. of chloride of sodium is indicated. We now measure 
off with a pipette 30 cc. of the mixture of baryta and urine, 
render the reaction feebly though distinctly acid by a few drops 
of nitric acid and treat this with 2 x 17*5 cc. = 35 cc. of the silver 
solution. The whole volume of the mixture amounts to 65 cc; 
the precipitated chloride of silver is filtered off and half the 
mixed fluid, that is, 32*5 cc, in which there are 10 cc. of urine, 
is taken from the filtrate. 

The urea is now determined in this amount as is usual by 
the standard solution of mercury, in which, however, the dilu- 
tion resulting from the addition of the silver solution must be 
taken into account. (D, 2.) 

If the 32*5 cc. of the urine mixture taken for the titration of 



QUANTITATIVE ESTIMATIONS. 239 

the urea contained 2 per cent, of urea, 65 cc. of the mercury 
solution would be required. But if only 25 cc. were required, 
then according to D, 2, for (65 — 25) 40 cc. 0*8 cc. must be sub- 
tracted. Accordingly the urea must be calculated for only 
24-2 cc. 

Bautenberg's Method."^ Two specimens of 15 cc. each of the urine 
mixture are measured off. One is feebly acidulated with nitric 
acid, and the mercury solution, which serves for determining 
the urea, is allowed to flow into it until a permanent cloudiness 
appears. The number of cc. of the mercury solution used up 
to this point forms the correction for the chloride of sodium, 
and is taken into account in subtraction. (See § 13, C, 3.) The 
second specimen is used for precipitating the urea. The mer- 
cury solution is allowed to gradually flow in without previously 
acidifying, and the mixture is kept neutral by successive addi- 
tions of pure precipitated calcic carbonate. In order to deter- 
mine whether all of the urea is precipitated, a large drop of the 
mixture is placed by means of a glass rod on a clean glass plate 
covered thickly on its under side with asphaltum varnish, and 
it is covered with a drop of bicarbonate of sodium stirred up 
with water ; the appearance of the first distinct traces of a yel- 
low color indicates the end of the reaction. By using the 
bicarbonate of sodium the disturbing influence of the corrosive 
sublimate which is formed is entirely obviated, so that the 
urine can be accurately titrated up to one or two mgrm. of urea. 
The bicarbonate, however, must contain no normal carbonate, 
and must, therefore, before using be washed with small amounts 
of water after being rubbed up finely, until it no longer browns 
turmeric paper. 

4. The Urine contains Albumen. 

If the urine contains albumen, the urea cannot be directly 
determined by the method given, but the albumen must first 
be removed. The usual procedure, therefore, suffers the fol- 
lowing modification : 

100 to 200 cc. of urine are heated in a closed vessel on a 
water bath, until a complete coagulation of the albumen has 
taken place and thick flocculi have separated, so that the 
urine appears clear. If the coarse flocculent precipitate does 

*Annalen d. Chem. u. Pharm., Band 133, p. 55. 



240 ANALYSIS OF THE URINE. 

not form from lack of free acid, acetic acid is carefully added 
drop by drop to the hot fluid until it has taken place. Heating 
for half an hour is amply sufficient. Then after the fluid con- 
taining the coagulated albumen has become cold, it is filtered 
and the clear filtrate is used to estimate the urea, phosphoric 
acid, etc. 

5. The Urine contains Carbonate of Ammonium. 

Since the carbonate of ammonium in urine comes from de- 
composed urea, it may be of interest under certain circumstances 
to estimate the amount of urea, which corresponds to the car- 
bonate of ammonium. Liebig found that foul ammoniacal urine, 
when decomposition had not gone too far, frequently gave the 
same results as fresh urine. If in such a urine a precipitate 
which contains two equivalents of mercuric oxide to one equiv- 
alent of ammonia occurs after the addition of mercuric nitrate, 
an equal amount of mercuric oxide is required for decomposed 
as well as for unde composed urea, since the latter in its decom- 
position yields two equivalents of ammonia. (One equivalent of 
urea to four equivalents of mercuric oxide.) Investigations 
which were undertaken, however, showed that this relation did 
not remain constant, and that frequently more of the mercury 
solution was required. If, therefore, we wish for accurate re- 
sults, the ammonia and urea must be determined separately, 
and the former must be recalculated for urea. There are two 
ways to do this : 

a. One portion of the urine is precipitated with the baryta 
solution, a volume of the mixture corresponding to 10 cc. of 
urine is heated on the water bath until the ammonia is expelled, 
and the urea is then estimated as usual. In a second portion 
not treated with baryta solution the ammonia is determined 
volumetrically with a standard sulphuric acid solution, each cc. 
of which corresponds to 11 "32 mgrm. of ammonia or 20 mgrm. 
of urea. (500 cc. of such an acid must contain 16'333 of mono- 
hydrate d sulphuric acid.) 

b. A definite volume of the urine treated with baryta solution 
is distilled, and the ammonia which passes over is collected in 
a known volume of standard sulphuric acid. By means of a 
standard sodic hydrate, which is of corresponding strength to 
the sulphuric acid, the rest of the acid is titrated back, and 
the number of cc. saturated by ammonia thus found is calcu- 



QUANTITATIVE ESTIMATION'S. 241 

lated for urea. One cc. of sulplmric acid corresponds to 20 
mgrm. of urea. The results by tliis second method are more 
exact than by the first. 

Kletzinsky found by a series of comparative investigations 
that small amounts of other nitrogenous substances besides 
urea were precipitated from the urine by mercuric nitrate, so 
that naturally the amount of urea fell a little too high. These 
unknown substances may be separated by precipitation with 
a solution of sugar of lead and their disturbing influence re- 
moved. On the average this error amounts to about two per 
cent., for Kletzinsky obtained as a mean of several urea estima- 
tions, which he performed once in the ordinary manner and 
again after jDrevious precipitation with sugar of lead, 0.593 
grm. of urea in 10 cc. of urine instead of 0"580 grm. This error 
is so small, that in ordinary urinary analysis the tedious pro- 
cess of precipitating the urine previously acidulated with acetic 
acid with a solution of sugar of lead may safely be omitted. 
These substances are also said to yield ammonia on boiling 
with sulphuric acid, and to have a disturbing influence on the 
urea determination by the method of Eagsky and Heintz." 

If the urine contains sarkosin, as is the case after the internal 
use of this substance, the precipitation of the urea present at 
the same time is completely prevented, both in the neutral as 
well as in the alkaline solution. (E. Baumann and J. von Mer- 
ing.) t The same is true, according toE. Salkowski,t of methyl- 
hydantoin, and according to Schultzen and Nencki of acetamid 
also. If a solution containing equal molecules of urea and sar- 
kosin or methylhydantoin is titrated, at first no precipitate 
occurs ; but if the titration is carried farther, the end reaction 
occurs far later than would be caused by the urea jDresent; 
indeed, the latter appears to be present in double the amount 
that it really is. (E. Salkowski.) In these cases Liebig's method 
is wholly useless. 

Lastly, the fact should be remembered that allantoin also, 
like urea, is precipitated by mercuric nitrate. The method de- 
scribed above, therefore, will cause an error when allantoin 
occurs in the urine also. The error which is caused by the con- 

^ Prager Vierteljaliressclirift, 1855, ii. p. 83. 

f Bericlite d. deutscli. chem. Gesellscliaft, Band 8, p. 588 und 639. 

1 Ibid. 

^ 16 



242 



ANALYSIS OF THE URINE. 



Fig. 38. 



stant presence of kreatinin in tlie urine, is more perceptible, 
though always less, for, as I have found, this body is also pre- 
cipitated by mercuric nitrate. The daily quantity of kreatinin 
amounts to 0*8 to 1 grm. under normal circumstances. 

The excellent methods for the quantitative determination of 
urea given by Heintz^" and Eagsky,t as well as by Bunsen,t 
are not, however, entirely free from these and similar sources 
of error, and since they are considerably more detailed and de- 
mand more time than Liebig's method, they are employed in 
practice less frequently. 

ESTBIATION OF UrEA BY THE KnOP-HuFNER MeTHOD.§ 

A. Principle. As was mentioned above 
under urea, § 2, D, 7, hypobromite of so- 
dium decomposes urea into carbonic acid, 
nitrogen, and w^ater. The carbonic acid 
is very quickly absorbed by the lye, so 
that the urea can be quantitatively de- 
termined by the direct measurement of 
the nitrogen. One grm. of urea yields 
370 cc. of nitrogen measured at 0" C, 
and 760 mm. barometric pressure. 

B. Preparation of the Solution of Hypo- 
hromite of Sodium. 100 grm. of sodic hy- 
drate are dissolved in 250 cc. of water, 
and 25 cc. of bromine are added after the 
solution has become perfectly cold. 50 
cc. of this solution, diluted with 200 cc. 
of water, are sufficient to develop 130 to 
150 cc. of nitrogen from a chloride of 
ammonium solution. 

C. Performance. The decomposition 
of urea takes place very well in Huf- 
ner's apparatus, shown in fig. 28. A 

bellied vessel holding about 100 cc. is in solid connection with 
a small vessel, a, which holds at most from 5 to 8 cc, by 




^Poggend. Annal., Band 66, p. 114. 
•{• Annalen d. Chera. u. Pliarm., Band 56, p. 29. 
:{; Annalen d. Cliem. u. Pliarm., Band 65, p. 375. 
§ Journ. f. pr. Chem., N. F., Band 3, p. 1. 



QUANTITATIVE ESTIMATIONS. 243 

means of a tolerably wide moutli of 1*5 cm. in diameter. Be- 
tween the two, at h, there is inserted a tightly-fitting glass stop- 
cock, with a bore 8 or 10 mm. wide. The upper, smaller end 
of the larger vessel, d, is tightly surrounded by the neck of a 
glass dish, k, which has a Avidth of 1 dm. and a depth of 4 or 5 
cm., and rises up into its centre about 1 cm. This end also ex- 
tends into the opening of a eudiometer, e, which stands over it. 
The eudiometer is about 30 cm. long, 2 cm. wide, and is di- 
vided into \ cc. The whole apparatus is properly attached to an 
iron stand,/,/. 

The operation is now carried out as follows: "With the 
aid of a funnel having a long neck, the glass, o, together with 
the bore of the stop-cock, is filled with the urea solution, 2 
or 3 cc. of urine being quite sufficient; 10 cc. of urine are 
diluted to 40 or 50 cc, and from 8 to 12 cc. of this dilute urine 
are used for each analysis. The cock is then closed, and a 
mixture of equal parts of lye and distilled water is poured into 
the larger vessel, c, up to the edge. In the dish, k, there is 
placed a layer of saturated chloride of sodium solution, or, 
better still, the same bromine lye, 2 cm. deep, which serves 
as a shutting-off fluid. During this time only a few air bub- 
bles are evolved from c; when they have disappeared, the eudi- 
ometer filled with water is turned upside down over d, and, 
when it is fastened, the reaction may commence. The stojD- 
cock, h, is now turned at once, and the two fluids are thus 
brought together suddenly. The heavy lye quickly sinks into 
the lower vessel and brings about decomposition of the urea 
with active evolution of nitrogen wdiich collects in the eudiome- 
ter. If an accurate determination is not required, the ex- 
periment may be interrupted after five minutes ; in the other 
case it is advisable to wait a few hours. The eudiometer is 
then taken from the dish, A", its opening closed with the thumb, 
and it is carried to a cylinder filled with water and treated in 
measuring the gas according to Dumas's rule for the determina- 
tion of nitrogen. 

It is well to employ Knop's lye as fresh as possible. 

The calculation is carried out according to the following 
formula, since 1 grm. of urea yields 370 cc. of nitrogen at 0° C. 
and 760 mm. pressure : 



244 AWALYSIS OF THE URINR 

100 V {h-l)') 



V 



760-370. «(1 + 0-003665 r.) 



a = the volume of urine employed. 

v = the volume of gas read off. 

b = the height of the barometer. 

t = temperature. 

b'= the tension of aqueous vapor for the temperature t. 

Of the other constituents of the urine, uric acid and kreatin 
also give up a portion of their nitrogen; but with the small 
amounts of these substances which the urine contains the error 
caused by them is very small. 

Ivon- produced the decomposition in a simpler apparatus. 
It consists of a small glass tube 40 cm. high, which is divided 
into yV cc, and has a glass stop-cock at its upper part, above 
which there is a short piece of tubing of the same diameter, also 
divided. The apparatus is open at both ends. To determine the 
urea the lower end is sunk into a cylinder of mercury wide at 
the top ; then 2 or 3 cc. of urine are placed in the upper part, 
and by opening the stop-cock it is allowed to flow into the 
lower part ; it is afterward washed wdth a little sodic hydrate 
and the upper piece of tubing is filled with a solution of hypo- 
bromite of sodium. (Ivon uses the following solution : 30 grm. 
of sodic hydrate, 5 grm. of bromine, and 125 grm. of water.) If 
this is allowed to flow into the lower receiver by a quick but 
careful turning of the stop- cock, the development of gas begins 
immediately and is finished after ^\e or six minutes. The ni- 
trogen is then measured as above, reduced for pressure and 
temperature, and calculated for urea. 

This method excels from its great simplicity, rapid per- 
formance, and sufficient accuracy. 

Bunsen's Method modified by G. BuNGE.t 

50 cc. of urine are mixed with 25 cc. of an ammoniacal solu- 
tion of chloride of barium as concentrated as possible ; it is 
filtered through a dry filter, and 15 cc. of the filtrate, corre- 
sponding to 10 cc. of urine, are put into a strong glass tube 
sealed at the bottom, and containing about 3 grm. of solid, pure 

•^Buletin de ]a Societe cliim. de Paris, 19, p. 3. 
f Zeitschrif t f . analyt. Cliem., Band 13, p. 128. 



QUANTITATIVE ESTIMATIONS. 245 

chloride of barium. In introducing the mixture of urine care 
must be taken to keep the walls above the fluid dry. The tube 
is then thoroughly sealed over a lamp an inch to an inch and a 
half above the fluid, and heated five or six hours to 200° C. 
After it has cooled, the upper part of the tube is broken off, 
the contents thrown on a filter and thoroughly washed with 
water. The glass tube, on the inside of which small portions 
of carbonate of barium are frequently firmly adherent, is also 
thoroughly washed out, the whole amount of the carbonate of 
barium is dissolved in hydrochloric acid, filtered if necessary, 
and the barium precipitated by sulphuric acid as barium sul- 
phate. After a time the sulphate of barium is collected on a 
filter, washed, ignited, and weighed. In the above treatment 
the urea is decomposed according to the following formula : 

€H4N,a + H^a = €0, + 2NH3 
[C^H.N^O, -f 2H0 =200^ + 2NH3]. 

A molecule of BaS04 corresponds, therefore, to a molecule of 
urea. 233 parts by weight of barium sulphate correspond to 
60 parts by weight of urea. 

The extractive matters of the urine have no influence. But 
albumen and sugar heated with water to 200° C. develop large 
amounts of carbonic acid; when the urine contains albumen 
and sugar, therefore, the method is not applicable. (Hoppe- 
Seyler.) 

§ QQ. Estimation op the Chlorine (Chloride of Sodium). 
I. mohr's method. 

A. Principle. The principle of this method is easily understood. 
The urine filtered and acidulated with nitric acid is treated with 
a standard solution of nitrate of silver as long as a precipitate 
is produced ; but it is difiicult to hit this point exactly without 
filtering, wherefore the method loses a little in convenience and 
accuracy. Mohr proposed, therefore, to add a few drops of a 
solution of neutral chromate of potassium in the titration of 
fluids containing chlorine, and then to perform the analysis as 
usual. The end reaction with this modification manifests itself 
in a beautiful and striking way, since, when all of the chlorine is 
precipitated by the solution ai nitrate of silver, the next drop 



246 AI^ALTSIS OF TEE URINE, 

gives a beautiful red precipitate of clir ornate of silver. But this 
change requires neutral or at least faintly alkaline fluids, and 
on no account should there be any free acid present on account 
of the ready solubility of the chromate of silver in acids. 
But though this method is admirable in j^ure fluids containing 
chlorine, in its application to the urine considerable difiiculties 
are encountered, which are caused by the necessity of its having 
a neutral reaction. Many comparative experiments which I con- 
ducted first by Liebig's method, then by Mohr's, and finally 
gravimetrically, gave me always too high a result when titrated 
with a nitrate of silver solution after the addition of chromate 
of potassium. The reason of this is readily seen. If the titra- 
tion is carried out exactly according to Mohr's method, and a 
few drops of a solution of chloride of sodium are now added 
until the color of the fluid has become pure yellow again, in 
order to decompose the chromate of silver, the precipitate which 
is formed now is not pure chloride of silver. If, the light hav- 
ing been shut off, it is filtered, and after washing treated with 
cold dilute nitric acid, it becomes colored, and a not inconsider- 
able amount of silver may be detected in the filtrate by hydro- 
chloric acid. There is no doubt that oxide of silver in a neutral 
fluid is precipitated by coloring and extractive matters, and 
also by uric acid, wherefore an inexactness of the method must 
be the result. Phosphoric acid does not disturb the result, 
since chromate of silver is precipitated before the phosphate. 
(Compare § 13, C, 4) (Analytical Experiments.) 

Even in acid solutions the coloring and extractive matters, 
etc., are not wholly without influence, and I prefer, therefore, to 
completely destroy these substances according to Mohr's propo- 
sition by evaporating the urine after the addition of a little pure 
nitrate of potassium and heating the residue to a dull red heat. 

B. Prejmration of the Solutions, 

1. Standard Nitrate of Silver Solution. This solution must 
contain 18*469 grm. of silver to the liter, so that each cc. corre- 
sponds to 10 mgrm. of chloride of sodium or 6*065 mgrm. of 
chlorine. Therefore 18*469 grm. of chemically pure silver are 
dissolved in nitric acid, the solution is evaporated to dryness 
on the water bath, heated until all of the free nitric acid is re- 
moved, the residue taken up with distilled w^ater, and the solu- 
tion thus obtained diluted to a liter. If chemically pure fused 



QUANTITATIVE ESTIMATIONS. 247 

nitrate of silver is at our disposal, we can simply weigh off 
29*075 grm., dissolve it in water, and dilute it to a liter. 

2. Chromate of Potassium Solution. A cold saturated solu- 
tion of neutral chromate of potassium. 

C. Performance in Urine, 

5 or 10 cc. of urine are introduced into a small platinum dish, 
1 or 2 grm. of nitrate of potassium free from chlorine are 
added, and it is evaporated to dryness on the water bath. The 
residue is then heated over a free flame at first gently, after- 
ward stronger, until the carbon is completely oxidized and the 
residue is obtained as a white, fused, saline mass. The opera- 
tion readily and surely succeeds in this way, since the great 
excess of nitrate of potassium greatly diminishes the deflagra- 
tion, which is otherwise violent. The perfectly white saline 
mass is then dissolved in a little water, the solution is turned 
into a beaker, and the platinum dish carefully rinsed with water 
from a wash bottle. Yery dilute pure nitric acid is added drop 
by drop to the alkaline fluid until a feebly acid reaction has 
resulted, which is then neutralized by as much precipitated 
calcic carbonate as can be contained upon the point of a knife. 
The excess of calcic carbonate is not filtered off before the titra- 
tion, since it in no wise prevents the end reaction. Two or 
three drops of the solution of chromate of potassium are added 
to the mixture, and then the neutral silver solution is allowed to 
flow into it with constant stirring, until a distinct reddish tinge 
is produced, which is permanent also after stirring. The reac- 
tion is very beautiful ; the fluid, at first of a light canary-yellow 
color, shows in the places where the silver solution falls red. 
spots which disappear on stirring as long as chloride of sodium 
is still present. But as soon as the latter is completely decom- 
posed by the addition of the silver solution, the next drop shows 
a permanent reddish tinge of chromate of silver, which indicates 
the end of the experiment. 

Each cc. of the silver solution used up to this point indicates 
10 mgrm. of chloride of sodium or 6*065 mgrm. of chlorine. If, 
for example, to 5 cc. of urine we have used 5 cc. of the solu- 
tion of silver, they contain 50 mgrm. of NaCl, and 1,000 cc. of 
the urine, 10*0 grm. NaCl or 6*065 grm. chlorine. 

Pribram^ destroys the organic matters at a boiling tem- 

* Zeitschrift f iir analyt. Cliemie, Band 9, p. 428. 



248 ANALYSIS OF THE URINE. 

perature with permanganate of potassium. 10 cc. of urine are 
heated with 50 cc. of permanganate of potassium solution (1 or 
2 grm. of the salt in a liter), and the chlorine in the filtrate is 
determined as usuaL I have not obtained good results by this 
method. In my experiments 10 cc. of normal urine often de- 
composed four times as much chemically pure permanganate of 
potassium as Pribram states. There is found in this way, as is 
easy to prove, a considerable amount of oxalic acid, and the 
titration Avitli the silver solution not rarely gave, especially in 
concentrated urines, considerably more chlorine in the clear, 
tolerably dilute filtrate than the method described above, which 
I, therefore, unconditionally prefer. (Analytical Experiments.) 

Liebig's method * of estimating chlorine with mercuric ni- 
trate, aside from the fact that in many cases it fails, unless car- 
ried out very exactly, frequently gives absolutely erroneous 
results. In regard to easy manipulation and certain success, it 
is far behind the method with silver; therefore I content myself 
with referring to the original treatise in regard to it. 

1. Modification in Urine containing Iodine and Bromine. 

On account of the readiness with which the iodide and bro- 
mide of potassium go over into the urine, these substances 
must be considered in an accurate estimation of the chlorine. 
According to Salkowski, this error is most easily avoided as 
follows : 10 cc. of the urine are evaporated with nitre as usual, 
and ignited, the residue is dissolved in water, acidified with 
sulphuric acid, and the iodine removed by shaking with bi- 
sulphide of carbon. If the nitrite which forms on fusing does 
not suffice to set free all of the iodine present, it is advisa- 
ble to add a few drops of a solution of nitrite of potassium to 
the acidulated urinary fluid before it is shaken with bisulphide 
of carbon. The aqueous solution is finally neutralized v/itli 
carbonate of sodium, evaporated and titrated with nitrate of 
silver as usual 

II. METHOD OF J. VOLHARD AND A. FALCK. 

A. Principle. This method is founded on the behavior of sol- 
uble sulphocyanides toward solutions of silver and ferric salts. 
Soluble sulphocyanides produce in silver solutions a white pre- 
cipitate similar to chloride of silver, which is insoluble in dilute 

* Annalen d. Cliem. u. Pharm. , Band 85, p. 297. 



QUANTITATIVE ESTIMATIONS. 249 

nitric acid. A like precipitate of snlpliocjanide of silver with 
a solution of nitrate of silver is given by the blood-red solution 
of sulphocyanide of iron, and the color of the latter at last com- 
pletely disappears. If, therefore, a solution of sulphocyanide 
of potassium is added to an acid solution of nitrate of silver to 
which a little ferric sulphate has been added, every drop of the 
sulphocyanide solution at first produces a blood-red cloud, 
which, however, quickly disappears again on stirring, while the 
fluid becomes milk-white. It is not until all of the silver is 
precipitated that the red color of the sulphocyanide of iron re- 
mains permanent, and at the same time the end of the experi- 
ment is reached. The reaction is extremely delicate, so that 
this method is not inferior to the first in point of sensitiveness, 
and it has the advantage that the titration can be undertaken 
in an acid solution. 

B. Preparation of tlie Solutions. 

1. Standard Nitrate of Silver Solution, Description, see § QQ, 
1, B, 1. Each cc. corresponds to 10 mgrm. of chloride of so- 
dium or 6*065 mgrm. of chlorine. 

2. Solution of Iron Oxide. A cold saturated solution of crys- 
tallized ferric alum free from chlorine, or a solution of ferric 
sulphate, which contains about 50 grm. of iron oxide in the liter, 
is used. 

3. Standard Solution of Sulpliocyanide of Potassium. Since sul- 
phocyanide of potassium cannot be easily weighed accurately, 
10 grm. are dissolved in a liter of water and this solution is 
standardized by the silver solution. For this purpose 10 cc. of 
the silver solution are measured off, 5 cc. of the iron solution 
are added, and then pure nitric acid is added drop by drop until 
the mixture appears colorless. If the sulphocyanide of potas- 
sium solution is then allowed to flow into it from a burette, 
every drop at first gives a blood-red color, which immediately 
disappears on stirring. When all of the silver is precipitated 
as sulphocyanide of silver, the next drop of the sulphocya- 
nide of potassium solution gives a permanently red color to the 
fluid which indicates the end of the experiment. If, for example, 
to 10 cc. of the silver solution 9*6 cc. of the sulphocyanide of 
potassium solution have been used before the red coloration is 
permanent, 960 cc. of the latter are measured off, and this is 
diluted with 40 cc. of water to make a liter. Both solutions 



250 AJSTALYSIS OF THE URINE. 

must now be equivalent, wliich is to be determined by titrating 
again. 

C. Performance of the Analysis icitli Urine. 5 or 10 cc. of 
urine after the addition of 1 or 2 grm. of nitrate of potassium 
free from chlorine are evaporated and ignited as mentioned 
above, § QQ, 1, 0. Since the nitrous acid which is formed in 
this operation prevents the end reaction, the fused saline mass 
is dissolved in water, acidulated with nitric acid, and then the 
chlorine is 23recipitated with an excess of the standard silver 
solution. After this mixture has been warmed on the water 
bath for a time to completely remove the nitrous acid it is al- 
lowed to cool, 5 cc. of the iron solution are added, and then 
sulphocyanide of potassium solution equivalent in strength to 
the silver solution is added while constantly stirring until the 
excess of the silver added is precipitated, wliich point is recog- 
nized by the permanent red color of the mixture. The differ- 
ence then between the number of cc. of the silver and sulpho- 
cyanide solutions corresponds to the chlorine contained in the 
urine. If, for example, at first 12 cc. of the silver solution were 
added to 10 cc. of urine, and 4 cc. of the sulj)liocyanide solution 
were required to titrate back the excess, the amount of chlorine 
in the urine corresponded to 12 — 4 = 8 cc. of the silver solution 
= 8*0 grm. of chloride of sodium or 4*852 grm. of chlorine in 
the liter of urine. 

§ 67. Estimation of Phosphoeic Acid. 

A. Frinciple. If a hot solution of a phosphate dissolved in 
water or acetic acid is treated with a solution of acetate or 
nitrate of uranium, when free acetic acid is present, a precipi- 
tate of the phosphate of uranium occurs at once. If the solu- 
tion contains salts of ammonium in large amount, the precipitate 
also contains ammonia. The phosphate of uranium thus pre- 
cipitated contains 80*09 parts of uranium oxide to 19*91 parts 
of POi, and appears as a whitish-yellow precipitate with a faint 
greenish tinge, which is completely insoluble in water and acetic 
acid, but is soluble in the mineral acids. Since the precipitate 
is slimy and does not easily settle, the end of the reaction can- 
not be perceived in the fluid by stopping the precipitation ; 
therefore, to ascertain whether all of the phosphoric acid is 



QUANTITATIVE ESTIMATIONS. 251 

precipitated, a slight excess of uranium oxide must be added, 
which can be detected with ease by the very delicate reaction 
of the uranium salts with ferro cyanide of potassium. Uranium 
salts, as is well known, give a reddish-brown precipitate with 
ferrocyanide of potassium, by which the slightest traces of 
uranium oxide are indicated by a corresponding reddish-brown 
coloration of the fluid. The uranium oxide once precipitated is 
not decomjDosed by ferrocyanide of potassium, as is the freshly 
precipitated ferric phosphate ; therefore to test for an excess of 
uranium a drop of the mixture may be brought directly in con- 
tact with the solution of ferrocyanide of potassium. If there is 
no free oxide of uranium present, the mixture does not become 
colored, but the slightest excess of oxide of uranium is most 
certainly recognized by a corresponding red color. Moreover, 
phosphate of uranium is a perfectly stable compound, and in 
a solution containing an excess of uranium does not, like ferric 
phosphate, change into a more basic compound; therefore, 
when the end reaction has once distinctly occurred, it may be 
produced again even after standing for days, which by the old 
method with ferric chloride was not the case even after a few 
minutes, for which reason the latter method is highly unsatis- 
factory and faulty. 

In the presence of acetate of sodium, however, the reaction 
of the ferrocyanide of potassium on uranium salts is not so 
delicate as in pure aqueous solutions. It is easy to be convinced 
of this if 50 cc. of water and 50 cc. of a solution of acetate of 
sodium, which contains 0'5 gram of the latter and 1 gram of 
free acid, are treated side by side with 0*2 cc. of the same solu- 
tion of uranium and both tested with ferrocyanide of potassium. 
The distilled water will immediately show a very distinct brown 
color, while the solution of acetate of sodium gives a much 
feebler reaction, which gradually grows darker after a time. If 
the amount of acetate of sodium is large, the reaction at first 
entirely fails and appears only after a long time on the further 
addition of ferrocyanide of potassium. 

This circumstance is of the greatest importance^ since in the titra- 
tion of phosphoric acid with uranium salts {for example, in 50 cc. of 
urine) sometimes more and sometimes less acetate of sodium is added, 
so that sometimes more and sometimes less uranium sohdion icill le 
required with the same amount of phosphoric acid to ohtain the end 



252 ANALYSIS OF THE URINE. 

reaction ivitli ferrocyanide of potassiumy and an error will thus le 
committed, ivliicli, Jioivever, is readily olviated hy alivays taking a 
like volume of fluid and treating this constantly ivith the same amount 
of acetate of sodium lefore the titration. 
B. Preparation of the Solutions, 

1. Standard Phosphoric Acid Solution. It is well to have this 
of such a concentration that 50 cc. of it contain O'l gram. PO5, 
so that it approaches normal urine in regard to the amount 
of phosphoric acid as nearly as possible. It can be readily 
prepared from chemically pure, well-crystallized phosphate of 
sodium which has not been exposed to the air. The pure crys- 
tals are rubbed very fine, dried by pressing between filter paper, 
10 '085 grm. are accurately weighed off, and dissolved to a liter. 
50 cc. then contain exactly 0*1 grm. PO5. 

2. Solution of A cetate of Sodium. I have convinced myself by 
many experiments that 0*5 grm. of acetate of sodium is sufficient 
in all cases for 50 cc. of urine. Therefore 100 grm. of acetate 
of sodium are dissolved in 900 cc. of water, and this solution is 
brought uj) to a liter by 100 cc. of concentrated acetic acid. 
In the titration 50 cc. of urine are treated with 5 cc. of this acid 
solution of acetate of sodium. 

3. Uranium Solution. Pure commercial oxide of uranium or 
yellow double carbonate of uranium and sodium is dissolved in 
pure acetic acid, especially free from empyreumatic matters, the 
solution is diluted and it is standardized with the phosphate 
of sodium solution a. I have found it advantageous to so ar- 
range the uranium solution that 1 cc. of it precipitates and indi- 
cates only 0*005 grm. of phosphoric acid. 50 cc. of our solution 
of phosphoric acid a = O'l grm. of PO;, and therefore will need 
exactly 20 cc. of the uranium solution, which must contain first 
0*4023 grm. of oxide of uranium to precipitate the PO5, and 
second, a slight excess of oxide of uranium to indicate the end 
reaction. Therefore 50 cc. of the phosphoric acid solution a (0.1 
grm. PO5) are measured off, allowed to flow into a beaker, 5 cc. of 
the acid solution of acetate of sodium b are added to it, and it 
is heated on the water bath to 90^ or 100° C. The uranium so- 
lution is now allowed to flow into it, and it is tested after each 
^ cc. for the end reaction. For this purpose one or two drops 
of the mixture are spread out on a white porcelain surface, and 
then a small drop of a feebly yellow-colored solution of ferro- 



QUANTITATIVE ESTIMATIONS, 253 

cyanide of potassium is introduced into its centre by means of 
a slender glass rod. Even if there is only a trace of an excess 
of oxide of uranium in tlie mixture, a reddisli-brown island will 
form where the ferrocyanide of potassium solution is introduced, 
and, surrounded by the colorless or faint-yellow fluid, can be 
perceived with the greatest distinctness. I prefer this m.ethod 
to any other ; if after repeated testing and renewed addition of 
uranium solution a faint end reaction is finally obtained, it is 
again heated a few minutes on the water bath and tested once 
more. If now the reaction appears distinctly, the experiment 
is ended. 50 cc. of our phosphoric acid solution should re- 
quire 20 cc. of the uranium solution; each cc. of the latter 
should, therefore, precipitate and indicate 5 mgrm. of PO5. 
Supposing we had used 18*0 cc. of uranium solution to 50 cc. of 
the PO5 solution, we must add 20 cc. of water to every 180 cc. 
of the solution. Therefore one liter of the uranium solution is 
measured off, the necessary amount of water is calculated and 
added. In our case 111 '2 cc. of water must be added to 1,000 
cc. of the uranium solution, in order to obtain the desired con- 
centration. It is well, however, not to add the calculated 
amount of water at once, but a little less, test again with the 
phosphoric acid solution, and finally complete the uranium so- 
lution. If, for example, we have used the second time 19*8 cc. 
of the uranium solution to 50 cc. of the PO5 solution (01 grm. 
of PO5), we now add to every 198 cc. of the same 2 cc. of water, 
and make a new and thereby final test with the phosphate of 
sodium solution. Such a uranium solution, each cc. of which 
precipitates 5 mgrm. of PO5, and which at the same time con- 
tains a slight excess of oxide of uranium for the end reaction, 
must contain 20-3 grm. of pure oxide of uranium in the liter. 
(Equivalent of uranium = 60.) 

C. Performance ivitli the Urine. 

a. Estimation of the Total Phosphoric Acid. 

1. 50 cc. of urine, previously filtered, are put into a beaker, 
5 cc. of the acetate of sodium solution are added, heated on the 
water bath, and then the uranium solution is allowed to flow 
into it from a Mohr's burette divided into yV cc. When the 
precipitate no longer increases, which can be observed quite 
readily if the uranium solution is allowed to flow slowly down 
the side of the glass without stirring, the test is performed. 



254 ANALYSIS OF THE URINE. 

For this purpose one or two drops of tlie mixture are spread 
out on a white porcelain surface and a drop of a faintly yellow- 
colored solution of ferrocyanide of potassium is added to tlie 
centre of it by means of a slender glass rod. If there is a slight 
excess of oxide of uranium present, where the ferrocyanide of 
potassium solution is added an island of reddish-brown color 
is formed, which surrounded by the colorless or slightly yellow 
fluid may be observed with the greatest distinctness. If a 
feeble end reaction has taken place, the heat is continued for a 
short time (1 or 2 minutes) over the water bath and it is tested 
again ; if now the reaction remains distinct, if the coloi^ obtained 
corresponds to the tint at ivliicli the uranium solution ivas originally 
standardized, the experiment is ended. But in the other case the 
addition of the uranium solution is continued until the end 
reaction comes out distinctly and is permanent. But if through 
the careless addition of the uranium solution the proper end 
point shall have been exceeded, and therefore, if on the addi- 
tion of the ferrocyanide of potassium a deep brown color occurs 
immediately, then, according to circumstances, 10 or 20 cc. of 
urine are added to the mixture and the titration is continued 
with a more careful addition of the uranium solution until the 
right tint is reached. As was observed above, acetate of sodium 
retards the reaction of ferrocyanide of potassium with oxide of 
uranium, therefore the color gradually becomes darker, and 
care must be taken not to make a mistake. At all events 
we should accustom ourselves to regard the first very feeble 
brownish coloring in the centre of the drop, which can be brought 
out again in the same tint after further heating on the water 
bath (2 or 3 minutes), as the end of the experiment, though after 
the lapse of 10 or 15 minutes the brown color will increase in 
intensity. Pincus and Budecker, both of whom likewise pro- 
posed the oxide of uranium for the same purpose, perform the 
analysis in the cold, but I unconditionally prefer a hot fluid, 
since the complete separation of the phosphate of uranium takes 
place very much quicker in hot fluids. If to 50 cc. of urine, for 
example, 20 cc. of uranium solution have been required to pro- 
duce the feeble but permanent reaction on heating, it contains 
O'lOO grm. of PO5, which can readily be reckoned for the twenty- 
four hours' amount. 

2. The results are more exact wdien all of the phosphoric acid 



QUANTITATIVE ESTIMATIONS. 255 

is precipitated from tlie urine by a solution of magnesium, and 
tlie phosphoric acid is titrated as above in the washed precipi- 
tate. For this purpose 50 cc. of urine are precipitated with 
magnesium mixture (a clear mixture of sulphate of magnesium, 
chloride of ammonium, and ammonia), and are allowed to stand 
several hours for the complete separation of the precipitate. 
The ammonio-magnesian phosphate is collected on a small filter, 
washed with water containing ammonia (one part of ammonia 
and three parts of water), and after the filter has been broken 
through it is washed into a beaker. After heating on the 
water bath acetic acid is added, drop by drop, until it is com- 
pletely dissolved, it is diluted to 50 cc. with Avater, 5 cc. of the 
acetate of sodium solution are added, and the fluid is titrated 
with the uranium solution just as recommended above. This 
roundabout way is necessary only in the rarest cases, since the 
results are very satisfactory also when the urine is directly 
analyzed. Generally a few tenths of a cubic centimeter less of 
the uranium solution would be required by this second method 
in one and the same urine, which in the daily amount of urine 
of 1,500 cc. amounts to about 015 or 0*2 grm. PO^. 

b. Determination of the Phosphoric Acid combined icith the Al- 
kaline Earths. 

In order to determine only the amount of phosphoric acid 
combined with the alkaline earths, 100 or 200 cc. of the filtered 
urine, according to its concentration, are treated with ammonia 
until the reaction is alkaline, and it is then allowed to stand 
twelve hours. The earthy phosphates separated during this time 
are collected on a filter, and washed with water containing am- 
monia (one part of ammonia and three parts of water). When 
this is accomplished the filter is broken through, the precipi- 
tate washed into a beaker, and dissolved by the aid of heat in 
as little acetic acid as possible, and the phosphoric acid titrated, 
after 5 cc. of the acetate of sodium solution have been added 
and the whole volume has been brought to 50 cc, with the 
uranium solution as described under a. 

Example : 

50 cc. required 18 -4 cc. of the uranium solution for the precipita- 
tion of the total phosphoric acid = 0*092 grm. phosphoric acid. In 
1,000 cc. there were, therefore, 1-840 grm. To determine the phos- 



256 ANALYSIS OF THE URINE. 

plioric acid combined with the alkaline earths there were required for 
100 cc. of urine 6 cc. of uranium solution = 0-03 grm. of PO5. In 
1,000 cc. there were, consequently, 0*300 grm. 

The urine contains then 

a. Total PO3 =1-840 grm. 

b. PO5 combined with the earths ^0*300 " 



c. PO5 combined with the alkalies = 1*540 



§ 68. Estimation of the Degeee of Acidity. 

A. Principle. Since the acid reaction of a urine does not de- 
pend alone on the acid phosphate of sodium, but the presence 
of free acids may also contribute to it, as, for example, lactic 
acid, etc., we must be contented in estimating the amount of 
acidity to compare its powder of saturation with that of some 
known acid. Crystallized oxalic acid is selected for this pur- 
pose, and in this determination, therefore, we must establish 
how much oxalic acid the free acid present in a stated amount 
of urine corresponds to. "We gain our object by accurately 
neutralizing the known amount of urine with an alkaline solu- 
tion, each cc. of which corresponds to a fixed amount of oxalic 
acid ; sodic hydrate solution is best for this purpose, since it 
does not lose its efficacy by yolatilization as ammonia does, and 
at the same time it show^s the j)oint of neutralization very dis- 
tinctly. 

B. Prejiaration of the Solutions. 

1. Standrird O.calic Acid Solution. This serves us for stan- 
dardizing the sodic hydrate solution. It is prepared by dis- 
solving 1 grm. of pure oxalic acid which has not effloresced, and 
diluting it to 100 cc. Each 10 cc. of this solution contain 100 
mgrm. of oxalic acid. 

2. Tincture of Litmus. 3 grm. of litmus are digested for a long 
time with 20 grm. of water, and the deep blue solution obtained 
is filtered. 

3. Sodic Hydrate Sohdion. This is prepared as usual from 
carbonate of sodium and quicklime, and then its strength is 
determined with the oxalic acid solution, a. Each cc. must indi- 
cate 10 mgrm. of oxalic acid. 

10 cc. of the oxalic acid solution are accurately measured by 



QUANTITATIVE ESTIMATIONS. 257 

means of a pipette, it is allowed to flow into a small beaker, 
and is colored distinctly red by a few drops of the tincture of 
litmus. Tlie glass is then put on a white background, and the 
dilute sodic hydrate dropped into it until the fluid has become 
blue again. This point can be observed with the greatest dis- 
tinctness, since the transition of the red color to the blue takes 
place quite suddenly. Suppose that 6 cc. of the sodic hydrate 
solution have been required for this purpose, they correspond 
to 100 mgrm. of oxalic acid ; we therefore add 400 cc. of water 
to 600 cc. of the sodic hydrate and thus obtain a liter of alka- 
line solution, each cc. of which corresponds exactly to 10 mgrm. 
of oxalic acid. We now assure ourselves of the accuracy of our 
dilution by a second titration ; if the blue color takes place after 
the last drop of 10 cc. has been added, then the sodic hydrate 
may be used for determining the acid in the urine. 

C. Performance. 

On account of the color of the urine itself it is impossible to 
add the tincture of litmus directly to it in titration, since the 
change from red to blue cannot be observed with sharpness in 
a colored fluid. With urine, therefore, we must have recourse 
to litmus paper in order to determine the point of saturation, 
and must perform the analysis as follows : 

After 50 or 100 cc. of urine are measured off and introduced 
into a beaker, the standard sodic hydrate is added drop by 
drop. After each ^ cc. used, a drop of the fluid is taken out 
with a glass rod and placed on a small piece of sensitive blue 
litmus paper. If the spot where the drop lies becomes red 
after a few seconds, the addition of sodic hydrate is continued 
until no more reddening of the paper is observed. A drop is 
then put on red litmus paper, and if it is made blue, the 
volume of sodic hydrate which was used is noted, and the ex- 
periment is repeated with a new quantity of the urine, but a 
few drops less are added; by frequent testing the point of satu- 
ration is very accurately determined. 

§ 69. Estimation of the Sulphukic Acid. 

A. Principle. The method of estimating sulphuric acid de- 
pends simply on the addition of a solution of chloride of barium 
of known strength to a definite quantity of urine, as long as a 
17 



258 ANALYSIS OF THE TTRmE. 

precipitate of sulphate of barium is produced by it. But it is 
to be noticed tliat as soon as an amount of chloride of barium 
exactly equivalent to the quantity of sulphuric acid has been 
added to a fixed volume of urine feebly acidified with hydro- 
chloric acid, a so-called neutral point occurs in which the fil- 
trate shows a slight cloudiness, both with sul]3huric acid and 
with a solution of chloride of barium. In the solution thus 
formed chloride of potassium, chloride of barium, and sulphate 
of potassium must be considered to be in a certain condition 
of equilibrium ; now, if chloride of barium or sulphate of potas- 
sium is added, the equilibrium is destroyed and a precipitation 
of sulphate of barium results. In the titration of sulphuric 
acid in urine with a solution of chloride of barium, either the 
latter can be added until the neutral point is reached, that is, 
until in the filtrate both by another drop of the chloride of 
barium solution, and in another specimen by a drop of a solu- 
tion of sulphate of potassium, a faint cloudiness is produced, 
or until only a slight excess of barium is indicated in the fil- 
trate by sulphate of potassium. 

The solution of chloride of barium must naturally have a 
different concentration, according as the one or the other end 
reaction is chosen. If the titration is carried to the neutral 
point, it is well to make the solution of chloride of barium of 
such a strength that 1 cc. of it contains an amount of barium 
exactly equivalent to 10 mgrm. of sulphuric acid; but in the 
second case, the barium solution must contain a slight excess 
of barium for each cc. to precipitate 10 mgrm. of SO3 and to in- 
dicate the end reaction by a slight barium reaction in the fil- 
trate. I have convinced myself that the neutral point can be 
attained quite readily, and that the results when the titration 
is carried to this point are quite satisfactory ; and, therefore, I 
prefer to regard the titration of sulphuric acid as ended onco 
for all, when in two specimens of the clear filtrate an equally 
faint cloudiness is produced by chloride of barium and by sul- 
phate of potassium. Mulder first called attention to this neu- 
tral point, in the titration of a solution of silver by chloride of 
sodium. 

B. Preparation of the Solutions. 

1. Chloride of Barium Solution. This solution must be so 
concentrated, that 1 cc. of it precipitates exactly 10 mgrm. of 



QUANTITATIVE ESTIMATIONS. 259 

sulphuric acid. It is prepared simply by dissolving 30 "5 grm. 
of powdered, crystallized chloride of barium which has been 
dried in the air, and diluting the solution to a liter. 1 cc. then 
corresponds to 10 mgrm of anhydrous sulphuric acid. 

2. Solution of SidjDhate of Potassium, This must be exactly 
equivalent to the chloride of barium solution; it is prepared 
by dissolving 21*778 grm. of powdered, chemically pure, sul- 
phate of potassium dried at 100" C, and diluting the solution 
to a liter. 1 cc. then contains 10 mgrm. of sulphuric acid, and 
is exactly equivalent to the solution of chloride of barium. 

C Performance. 100 cc. of the urine to be examined are put 
into a narrow long-necked flask (fig. 29), treated with twenty or 
thirty drops of hydrochloric acid, and heated on the water bath ; 
then 5 or 8 cc. of the chloride of barium solution are allowed 
to flow into it from a burette and to stand until the sulphate of 
barium has settled. At a boiling temperature it becomes thick 
quite rapidly and then deposits very well. When the fluid has 
become clear another cc. of the chloride of barium solution is 
added, it is heated, and ten or twelve drops of the urine are fil- 
tered through a small filter the size of a thimble into a very small 
narrow test tube about two inches long, and tested to see if 
there is any further precipitation by the chloride of barium or 
not. If the latter is the case, a few drops of sulphate of potas- 
sium solution are added to a second specimen of the filtrate by 
which an excess of the baric chloride solution is shown. But if 
in the first specimen we still get a distinct cloudiness with the 
baric chloride solution, the fluid is poured back again into the 
flask, the filter and tube are rinsed with fig. ^m 29. 
a little water and this is added to the urine |||| 

also. If thus far about 8 cc. of chloride of pi 

barium solution have been used, 1, 2, 3, or ft | 

4 more are added, according to the intensity 1 I 

of the reaction, which by a little practice J "|i 

can readily be estimated by the degree of Bt \ 

cloudiness which takes place at the first m ^|l 

test, the whole is heated to boiling, a few Ife^ jSm 

drops are again filtered off for testing, and ^^mrn^ 

this is continued until at last there is no more cloudiness pro- 
duced in the filtrate by chloride of barium. If this is the case 
after using, for example, 13 cc, and if sulphate of potassium 



260 ANALYSIS OF THE UBINE. 

now in a new test sliows a distinct excess of barium, we know 
that tlie right point must lie between 12 and 13 cc, and the 
100 cc. of nrine must contain between 120 and 130 mgrm. of 
sulphuric acid. 

100 cc. of the urine are, therefore, measured off anew, treated 
with 20 or 30 drops of hydrochloric acid, 12 cc. of the chloride 
of barium solution are added immediately, heated, and a few 
drops of the filtrate tested with J^ cc. of the baric chloride solu- 
tion. If a distinct cloudiness takes place immediately, the fil- 
trate and the original fluid are united again, -f^ cc. more of the 
baric chloride solution are added, the filtrate is again tested, 
and this is continued till at last the chloride of barium solution 
shows only a very faint cloudiness after several seconds. If a 
second specimen of the filtrate is now tested with a few drops 
of the sulphate of potassium solution, it will be found that a 
slight cloudiness occurs here also after a few seconds, so that 
the neutral point is reached and the titration is ended. If we 
have used up to this point about 12*8 cc. of the chloride of 
barium solution, the 100 cc. of urine contains 0*128 grm. of SO.., 
from which the amount in twenty-four hours can be very easily 
reckoned. But if by an incautious addition of the chloride of 
barium solution the point has been far exceeded in the first 
experiment, a few cc. of the exactly equivalent sulphate of potas- 
sium solution are added, and the boundary is determined by a 
more careful addition of the baric chloride solution. The num- 
ber of cc. of the sulphate of potassium solution added must 
naturally be subtracted from the whole number of cc. of the 
baric chloride solution used, when making the calculation. 

Although the operation appears long it can be performed in 
half an hour very easily and gives satisfactory results. 100 cc. 
of urine contained 0*129 grm. of SO3 as determined by weighing, 
and by titration to the neutral point it was estimated to contain 
0128 grm. 100 cc. of another urine gave 0139 grm. SO,, deter- 
mined by weighing, and 0137 grm. SO3 by titration. (Analytical 
Experiments.) 

Gravimetric Determination. 

100 cc. of filtered urine are measured off with a pipette, it is 
allowed to flow into a small beaker, heated on the water bath, 
a little hydrochloric acid added, and then chloride of barium 
solution in slight excess. The sulphate of barium formed will 



QUANTITATIVE ESTIMATIONS. 261 

settle very quickly and the supernatant fluid will become clear. 
Tlie whole precipitate is collected on a small filter, the weight 
of whose ash is known, it is then washed with hot water until 
the wash water is no longer made cloudy by sulphuric acid, and 
dried as soon as the washing is finished. The sulphate of 
barium obtained must then be ignited ; it is, therefore, trans- 
ferred from the filter to a small weighed platinum _ crucible. 
After the filter has been ignited on the cover of the crucible, 
the cover is placed on the latter, taking care, however, that the 
ash does not come in contact wdth the precipitate, and it is ig- 
nited strongly for a short time. But since organic matters are 
always precipitated from the urine w^ith the sulj^hate of barium, 
a little sulphide of barium is formed on heating ; therefore after 
the crucible has become cold again its contents must be mois- 
tened with a few drops of dilute sulphuric acid and be heated 
once more until the excess of sulphuric acid is expelled. The 
crucible is then allowed to cool in a desiccator over sul- 
phuric acid and is afterward weighed. If the weight of the 
crucible and of the filter ash are subtracted from the total 
weight, we obtain as the difference the amount of sulphate of 
barium precipitated, from which it is easy to calculate the sul- 
phuric acid, since 100 parts of sulphate of barium correspond 
to 34'33 parts of sulphuric acid. 

§ 70. 
1. Estimation of Sugar by Fehling's Method. 

A. Principle. The method of estimating sugar in the urine is 
founded on its property, mentioned in § 25, D, 7, of precipi- 
tating the copper in the form of red cupreous oxide from alka- 
line solutions of sulphate of copper. If a copper solution of 
known strength is used, a fixed volume of which is exactly re- 
duced by a certain amount of grape sugar, we can easily accu- 
rately estimate the sugar contained in solutions of unknown 
strength, if we determine the volume wdiich is just sufficient to 
completely decompose a measured amount of the standard cop- 
per solution. 180 parts by weight of grape sugar ( = 1 equiva- 
lent) precipitate the copper from 1247*5 parts by weight of 
cupric sulphate (=10 equivalents). 



262 AI^ALYSIS OF THE URINE. 

B. Preparation of tJie Copper Solution. 

34:'639 grm. of pure crystallized sulpliate of copper are dis- 
solved in about 200 grm. of water ; on the other hand 173 grm. 
of crystallized chemically pure potassio-sodic tartrate are dis- 
solved in 500 or 600 grm. of sodic hydrate of specific gravity 
1'12, and the sulphate of copper solution is gradually added to 
this alkaline solution. The clear mixed fluid is then diluted to 
one liter. 10 cc. of this copper solution are exactly reduced 
by 0'05 grm. of grape sugar. If the copper solution is to be 
kept for a long time, it is absolutely necessary to place it in 
small bottles (40 to 80 grm.), which are to be closed with good 
stoppers, sealed, and then stored in a cool place. 

C. Performance. 

In order to obtain favorable results by this method it is a ne- 
cessary requisite that the urine to be tested for sugar as well as 
the copper solution shall be largely diluted. It is well to treat 
10 cc. of the copper solution with 40 cc. of distilled water, and 
to dilute 10 or 20 cc. of the urine, which has been previously 
filtered, to ten or twenty times its own volume, so that at most 
it contains J per cent, of sugar. 

Then after heating the measured and diluted 10 cc. of the 
standard copper solution in a small flask over a lamp nearly to 
the boiling point, the urine also diluted is added from a burette, 
at last drop by drop, until complete reduction has taken place, 
that is, until the fluid has become colorless. In doing this, 
however, there are many things to be heeded. As soon as the 
first drops of the saccharine fluid fall into the hot copper solu- 
tion, the separation of suboxide commences. The mixture ap- 
pears reddish brown with a greenish tinge on account of the 
suspension of the red cupreous oxide in the blue solution ; the 
greater the addition of the solution of sugar, however, the richer 
and redder the precipitate becomes, and it is not until the latter 
has assumed a deep red color and the fluid has become per- 
fectly colorless that the experiment can be regarded as finished. 

The analysis is performed most accurately and quickly as fol- 
lows : As soon as the mixture in the flask, on very gentle 
boiling, and after the repeated addition of the diluted urine, 
commences to assume a red color, the flask is removed from 
the flame and the separated cupreous oxide is allowed to settle, 
which occurs the more readily and quickly the nearer the 



QUANTITATIVE ESTIMATIONS. 263 

point of complete reduction of tlie cupric oxide is reached. 
The faintest trace of blue color may be observed with great 
sharpness, if the flask is brought between the eye and a win- 
dow, and the fluid viewed by horizontal transmitted light. If 
we are still far from the end reaction, as remarked above, the 
cupreous oxide already separated deposits more slowly, but 
the blue color can still be seen very distinctly by transmitted 
light if the mixture is given a rotary motion while we look 
through it. Finally, the more nearly the blue disappears from 
the fluid, kept very near the boiling point always, the more 
carefully must we allow the sugar solution to run in ; but at last 
a point appears after the repeated addition of the latter and 
continued heating, at which the last blue shimmer disappears 
with one or two drops of the sugar solution, and gives place 
to a very faint yellow tinge. The reaction is now finished, 
and all of the cupric oxide is reduced; nevertheless we can 
be certain by further tests. We, therefore, filter some of 
the boiling fluid into three test tubes ; one specimen of the 
absolutely clear filtrate is acidulated with hydrochloric acid 
and tested with sulphuretted hydrogen water, while a second 
specimen, after acidulating with acetic acid, is treated with fer- 
rocyanide of potassium. Neither of the two reagents should 
change the fluid ; the first, therefore, must not color it black nor 
the second reddish brown or precipitate it at all. If the two 
behave indifferently we may conclude that all of the copper 
is reduced and precipitated, and that we have added a suffi- 
cient amount of the solution of sugar. It is well to take this 
into consideration, however, that the cupreous oxide very 
quickly oxidizes again and dissolves, therefore in testing the 
fluid it must be filtered off immediately after the end of the ex- 
periment, while boiling, since after it has cooled it will always 
have a bluish color on account of the cupric oxide which has 
been dissolved again. 

If no more undecomposed cupric oxide is found by means of 
the above reagents, an error may nevertheless have been made 
by having added too much of the urine, so that naturally the 
amount of sugar will be calculated less than it really is. There- 
fore, the third specimen of the clear, almost colorless filtrate 
is treated with a few drops of copper solution and heated to 
gentle boiling. Even when only a trace of sugar has been 



264 ANALYSIS OF THE URINE. 

added in excess, after a short time there occurs a distinct red 
shimmer, which may be quite beautifully and readily appre- 
ciated by reflected light. When a great excess of sugar has 
been added the filtrate has a yellow color ; then there is nothing 
to do but to perform the analysis over again more carefully, 
which indeed is always to be advised as a test of accuracy. 

However, if the experiment is performed in a small flask in 
the manner described, as was first suggested by A. Ziegler, the 
right end point may be obtained with great accuracy with a 
little experience, as I have demonstrated. 

The volume of urine used contains, therefore, as was men- 
tioned above, 0*05 grm. of sugar. Now since the amount of 
sugar in the fiuid is inversely proportional to the volume used, 
to determine the per cent, of sugar in the urine, we must divide 
five by the amount in cubic centimeters of urine used, if it was 
not diluted ; but if, for example, it was diluted to twenty times 
its volume, we must divide 20 x 5 = 100 by the number of cc. 
used. 

Of the other constituents of urine it is probably the uric acid 
chiefly which is known to reduce the copper solution on boil- 
ing, and which may, therefore, influence the result. Fehling, 
for this reason, first precipitates the urine with basic acetate of 
lead. But Briicke disapproves of this precipitation, because, 
according to him, some of the sugar is precipitated at the 
same time. Pure fruit sugar produced from urine is, how- 
ever, not precipitated by basic acetate of lead, and it can at 
most, therefore, only be carried down mechanically. Fehling 
experimented with normal urine to which from 10 to 12 per 
cent, of sugar was added. But if we have a diabetic urine 
of about 8 per cent., when 10 cc. of it are diluted to 200 cc, 
we require to decompose 10 cc. of Fehling's solution only 12*5 
cc. of this diluted fluid corresponding to 0*6 cc. of the original 
urine. The uric acid contained in 0*6 cc. of diabetic urine 
would be a very small amount. 

I have made several experiments with diabetic urine in order 
to convince myself of its action. 

a. 10 cc. of urine were diluted to 200 cc. and directly used 
for analysis. In several trials l2"3 cc. were required. 

b. 10 cc. of urine were diluted with 188 cc. of water and 2 cc. 
of basic acetate of lead, which were more than sufficient to pro- 



QUANTITATIVE ESTIMATIONS. 265 

duce complete precipitation, were added. After twelve hours 
it was filtered, and exactly 12*2 cc. were used to 10 cc. of the 
Fehling's solution. 

c. 150 cc. of urine were left at rest for forty-eight hours at 
5^ or 6^ C. with 5 cc. of hydrochloric acid of I'l specific gravity. 
10*33 cc, corresponding to 10 cc. of the original urine, were 
filtered from the separated uric acid, diluted to 200 cc, and 
used for analysis. In several trials 12-3 cc were required. 

The same experiments were repeated several times with dia- 
betic urine of other days without any variation in the result 
worthy of mention by the different methods. But apart from 
this consideration, in many cases a precipitation with basic 
acetate of lead may be desirable, and when this is done in a 
urine previously diluted to at most 0*5 per cent., the amount of 
sugar precipitated will be none, or, at least, very slight indeed, 
as was determined by Fehling's experiments. If albumen is 
present, it must be removed; the urine is heated to boiling 
after the addition of a drop of acetic acid, the coagulum which 
forms is filtered off, carefully washed, and the filtrate obtained, 
diluted if necessary, is used for determining the sugar. 

2. Estimation of the Sugae by Knapp's Method.* 

A. Principle. This method depends on the complete reduc- 
tion of cyanide of mercury in alkaline solution to metallic mer- 
cury by means of grape sugar at a boiling temperature. 400 
mgrm. of cyanide of mercury require 10 mgrm. of anhydrous 
grape sugar. 

B. Preparation of the Solution. 10 grm. of pure dry cyanide 
of mercury are dissolved in water, 100 cc. of sodic hydrate of 
1*145 sp. gr. are added, and the mixture is diluted to 1,000 cc. 

C Performance. The analysis is performed as with Fehling's 
solution. 40 cc. of the cyanide of mercury solution are brought 
to the boiling point in a flask, and the urinary fluid containing 
about I per cent, of sugar is allowed to flow in until all of the 
mercury is precipitated. In the mixture of urine used we have 
had just 100 mgrm. of grape sugar. "When the sugar solution 
flows into the boiling alkaline solution of cyanide of mercury, 

* Annalen d. Chem. u. Pliarm., Band 157, p. 252. 



266 ANALYSIS OF THE URINE. 

the mixture immediately becomes turbid, but clears up toward 
the end of the operation and then assumes a yellow color. In 
order to follow the course of the operation, from time to time a 
drop of the mixture is put on a piece of the finest Swedish filter 
paper, which is placed over a small beaker containing a little 
of the strongest sulphide of ammonium. If a brown spot is no 
longer formed on the paper, the experiment is ended. The re- 
action is still more delicate when a drop is placed on a strip of 
Swedish paper, and then a drop of sulphide of ammonium on a 
glass rod is held over it for about half a minute. At first the 
whole spot becomes brown, but toward the end a light-brown 
ring only forms on its edge, which can finally be distinctly 
recognized only when the transparent spot is held up toward a 
bright light. The fresh transparent spot remains wholly un- 
changed by sulphide of ammonium vapor at last, so that with 
a little experience the titration can readily be carried within yV 
cc. of the one-half per cent, solution. If the spot is allowed to 
dry finally, a clear-brown ring of sulphide of mercury always 
appears, since a neutral point seems to be formed, as there 
always remains in solution a trace both of grape sugar and of 
cyanide of mercury, which is removed only by an excess of the 
one or the other. We must, therefore, regard the color of the 
fresli spot as the standard. For greater accuracy a few cc. of 
the fluid are at last filtered off, acidulated Avith acetic acid, and 
tested with sulphuretted hydrogen to see whether mercury is 
present or not. 

According to comparative investigations which my assistant, 
Mr. Pillitz, conducted with diabetic urine, Knapp's method 
gave results which coincided very well with Fehling's method. 
(Analytical Experiments.) The easy preparation of the solu- 
tion of cyanide of mercury and its absolute durability are de- 
cided advantages. 

3. Estimation of Sugar by Ciecumpolarization. 

a. With the Ventzke-Soleil Polarizer, 

A. The Polarizer. Fig. 30 shows the Soleil-Yentzke sac- 
charimeter A with the lamp which belongs with it. 

We will first consider the optical arrangement and then the 
employment of this ingenious apparatus. The light coming 



QUANTITATIVE ESTIMATIONS. 



267 



from the lamp B first falls on a large Nicol prism at ?, wliicli, 
with the quartz plate at h cut perpendicular to the axis, can be 
turned around the axis of vision by means of the cogwheels m 
and ^3 and the iron rod nm. At i there is a second fixed Nicol 
prism, and in front of it at h the soleil double plate made of 
quartz rotating to the right and left. In the front part of the 

Fig. CO. 




apparatus there is at (/ a left-handed quartz plate cut perpen- 
dicular to the axis, and in front of it a compensator made of two 
right-handed quartz prisms, which prisms can be so shifted by 
means of a driving gear on the head, o, that the polarized light 
which traverses the apparatus has to pierce a thicker or thin- 
ner layer of right-handed quartz. At d there is again a Nicol 
prism which can be turned around the axis of vision by a small 
key at e, and lastly at the head of the instrument at Ic there is a 
small telescope to enable every eye to distinctly see the double 
plate standing at li. Then the glass tube filled with the urine 
to be examined and closed at both ends with glass plates is in- 
serted between j^ and 7^. The compensation prisms at / sup- 
port above a scale and nonius, which are best so divided that 
the parts of the scale to the right of the 0-point directly give 
the per cent, of grape sugar in 100 cc. of urine, when the ob- 
servation is made in a tube 200 mm. long at 17° C. On the left 
of the 0-point a second scale gives under the same circum- 
stances the per cent, of albumen in 100 cc. of urine. If we 



268 ANALYSIS OF THE URINE. 

place the compensator at/, by means of tlie tliumb-screw o, in 
such a manner that the 0-mark of the nonius exactly corre- 
sponds with that of the scale, the two right-handed quartz prisms 
have together the same thickness as the left-handed quartz plate 
at g, and the two neutralize each other, so that the eye looking 
at a, when the two Nicol prisms at d and i are properly placed, 
will see the double plate h having exactly the same color. The 
same is the case if the examining tube is filled with distilled 
water and inserted between/^/;. If the two quartz prisms are 
now shifted to the right or left by means of the screw o, the 
two halves of the double plate h immediately appear unequally 
colored, just so if the compensator stands exactly on and the 
examining tube contains a fluid rotating to the right or left. 
If, for example, this is filled with diabetic urine, the compensa- 
tor must now be turned toward the right in order to restore 
again the deranged equality of color of the double plate. 
Lastly, it is of great importance to be able to give the double 
plate any shade of color desirable, since all eyes do not possess 
a like sensitiveness for all colors. For this purpose the back 
part of the apparatus situated next the lamp is of service. By 
means of the rod nm and the cogwheels m and j) the quartz 
plate at h and the Nicol prism I can be turned around the axis 
of vision ; the former, therefore, since it is between a fixed Nicol 
prism, z, and a movable one, 1, will run through all shades of 
color, and also allow only colored light to pierce the apparatus, 
by which the original color of the double plate may be varied 
at pleasure. 

Proper Arrangement of the Apparatus. First, the saccharimeter 
is so placed, as represented in fig. 30, that the brightest part 
of the illuminating lamp B sends the light through the lateral 
connecting tube r of the clay cylinder s, which has its outer 
surface blackened, directly in the axis of the apparatus ; then 
the observation tube, which has been exactly filled with distilled 
water, is placed between pp, and the compensator is so arranged 
that the 0-point of the nonius coincides with the zero-point of 
the upper scale. If we now observe at a, by shortening or 
lengthening the telescope he we soon reach the point at which 
the picture appears clear and well defined and the fine line 
which divides the double plate into halves becomes sharply 
defined. If the double plate appears absolutely isochromatic 



QUANTITATIVE ESTIMATIONS. 269 

and if the isocliromatism also remains in all the shades of color 
which we can give it by turning the rod nm, then the apparatus 
is in order ; in the other case the zero-point must be corrected. 
For this purpose everything is left unchanged except the Mcol 
prism at d, which is turned with the key at e a little to one side 
or the other, until the desired color of the two halves of the 
double plate has been attained. As a correction the scale is 
moved a little one way or the other by turning the screw o until 
the picture appears exactly isochromatic again. If we look at 
the scale and nonius now, the two zero-points must exactly co- 
incide ; in the contrary case a new adjustment must be made of 
the Nicol prism d. This correction, however, is only very 
rarely necessary ; if the instrument is carefully kept the zero- 
point remains constant for years. 

B. Process of Estimating Sugar. Diabetic urine can usually be 
directly examined in the polarizer if it is filtered so as to be ab- 
solutely clear. When the apparatus has been given the position 
shown in the figure, the 200 mm. long observation tube is filled 
with clear filtered urine, or urine which has been decolorized by 
animal charcoal if necessary, taking care, however, to avoid in- 
closing air-bubbles, and it is then laid between the points p and 
23 in the apparatus. Then after the telescope has been sharply 
focused, the compensator is turned until the two halves of the 
double plate appear nearly isochromatic, and those shades of 
color are sought, by turning the Nicol prism at I to the right or 
left with the rod nm, in which the slightest difference in the 
color of the two halves of the double plate is most distinctly 
perceptible. A pale rose will meet this purpose best ; at all 
events, we may soon convince ourselves that all dark, fervid 
colors which the double plate gradually assumes on turning the 
rod nm are wholly unserviceable. Frequent practice of the eye 
will soon enable us to hit upon the right one. We can now 
proceed to an accurate adjustment of the picture, isocliromatism 
of the two halves. The screw o is, therefore, seized, and the 
compensator moved back and forth until complete isochroma- 
tism of both halves is attained. The principal rule in this 
procedure is never to observe longer than ten seconds at a time.^ 

* The two glass plates wliicli close the observation tube must not be i)ressed 
on too closely, since they may themselves easily give rise to double refraction 
and show colors with polarized light, which cause the rotation produced by the 



270 ANALYSIS OF THE URINE. 

Since the eye quickly habituates itself to nice differences of 
color, an accurate result can never be arrived at by a single 
adjustment and too long an observation. 

When at last, after several observations, we think that the two 
halves of the picture are isochromatic, we again turn the prism 
at I with the rod nm ; if the two halves of the plate remain abso- 
lutely isochromatic in all the shades of color which the double 
plate now produces, then the experiment is finished; in the other 
case the compensator must be more accurately adjusted until at 
last the object aimed at is attained. The scale and nonius are 
now read off. The zero-point of the latter has removed consid- 
erably toward the right from the zero-point of the scale ; if it 
coincides with a mark of the latter, it shows with the obser- 
vation tube 200 mm. long as many per cent, of sugar in 100 cc. 
of urine as there are divisions from the zero-point of the 
scale to the zero-point of the nonius, since every line of the 
scale corresponds to 1 per cent, of sugar. If, however, the zero- 
point of the nonius lies between two divisions of the scale, we 
must seek a line of the scale of the nonius lying to the right 
which coincides with a line of the scale. When this is found, 
we count the divisions from the zero-point of the nonius to 
the one which coincides vrith the division of the scale inclu- 
sive. Each division on the nonius indicates yV P^r cent, of 
sugar. The whole per cents., therefore, are read off on the 
scale ; the tenths are read off on the nonius, for which a lens 
may be used with advantage. If the urine is too dark, the 
estimation is undertaken in an observation tube only 100 mm. 
long ; if it succeeds we have only to remember that every di- 
vision of the scale indicates 2 per cent, and every division of 
the nonius j% per cent, of sugar. But if we do not attain our 
object in this way we must decolorize the urine by means of 
animal charcoal, or a measured volume of the urine is precipi- 
tated with a known volume of sugar of lead solution, filtered, 
and the clear colorless filtrate is examined. Of course the dilu- 
tion caused by the solution of lead is to be taken into account 
in the estimation. 

C. The Urine also contains Albumen, If albumen is present 



urine wliicli is to be examiued, to appear more or less erroneous. (Zeitsclirift 
f. analjt. Cliemie, Band 8, p. 211.) 



QUANTITATIVE ESTIMATIONS. 271 

at the same time with sugar, it must be removed first, since, 
the reverse of sugar, it turns the plane of polarization to the 
left. The albumen in 100 cc. of urine is coagulated by heat- 
ing in a flask after carefully adding a little acetic acid, the 
fluid is filtered into a graduate and washed with water until the 
filtrate amounts to exactly 100 cc. again. After it has cooled 
it is examined with the polarizer. 

According to the comparative experiments of Tscherinoff " and 
my own considerable experience, there is no doubt that the 
figures obtained with the Ventzke-Soleil apparatus in diabetic 
urine often vary considerably from the chemical determina- 
tions. The difference may be either minus or plus. In the 
first case we must consider that the urine contains another re- 
ducing substance, but one which does not turn the plane of 
polarization, whether it is sugar optically inactive or some other 
substance, or that besides the ordinary grape sugar, which turns 
to the right, there is also a small amount of sugar or some other 
body which turns the plane to the left. In cases where only 
plus is the result, in my experience the rarer ones, we may 
assume that the diabetic sugar possesses, at least in part, a 
higher rotatory power than the ordinary grape sugar, or that 
another body is present which turns to the right but does not 
have a reducing action. (Analytical Experiments.) 

b. With the Polaristrobometer of Wild. 

Figs. 31 and 32 show Wild's polaristrobometer and the lamp 
which belongs with it. The brass column, F, stands on an iron 
tripod, E, and bears on its upper end the horizontally and ver- 
tically movable support, on one end of which is the polariscope, 
A, and on the other end the circular disk, K, with the Nicol- 
setting. The polariscope consists of a feebly magnifying tele- 
scope focused on infinity, before whose objective a double j)late 
of calc-spar is placed, while in the focus of the objective there 
is a diaphragm with cross-hairs. The double plate, according 
to the theory of Savart's polariscope, is made of two 3 mm. 
thick plates of calc-spar cut at 45° to the optical axis, and with 
their principal planes crossing at right angles. At the other 
end of the polariscope the analyzing Nicol prism is so inserted 
that its principal plane stands horizontally, and includes with 

" Zeitschrif t f. analyt. Chem., Band 6, p. 502. 



272 AJS'ALYSIS OF THE URINE. 

that of the double plate an angle of 45°. A screen, M, at the 
ocular, serves to keep off the disturbing side light from the eye 
of the observer. 

Finally, the polarizing Nicol is inserted in a shell, N, at the 
circle, K, a^nd on its mounting is afterward placed the dark 

tube D. 

The circular disk and Nicol may be turned by the knob, (7, 
by means of a toothed pinion. The index, 7, for reading off the 

Fig. 31. 




position of the circular disk is put on the support of the latter 
and has a simple mark. The telescope, P, serves for reading 
off its position, and its ocular, B, lies immediately beside the 
ocular. A, of the polariscope. The division is lighted by a 
movable perforated mirror, S, at the objective end of this tele- 
scope, and a candle or gas flame at the proper height serves 
as the source of light. 

One half of the circle contains a division marked with grams, 
which extends from the zero-point to about 300 toward the 
right and 150 toward the left. Each interval of this division 
corresponds to 1 grm. of pure cane sugar, which is contained 



QUANTITATIVE BSTIMATJOJ^S. 



273 



Fig. 32, 



in 1,000 cc. of solution, and when a tube 200 mm. long is used. 
On the opposite half of the circle, on the contrary, there is a 
second division into degrees and i of a degree (entire circum- 
ference 360 ), which serves to express the angle of rotation of 
the plane of polarization by any desired substances in an inde- 
pendent manner."^ 

Lastly, a special bed serves to receive the observation tube 
between the circular disk and the polariscope. 

The gram division mentioned depends on 
the use of a homogeneous source of light, 
and, indeed, a yellow light of the refrangi- 
bility of the line I). Fig. 32 shows the Bun- 
sen gas-lamp, which serves to produce this 
light. 

On the side arm, a, there is a small mova- 
ble wheel, Tf on whose spokes small glass 
tubes with platinum wire fused into them 
can be fastened. These wires contain beads 
of chloride of sodium, which are turned into 
the front edge of the flame by means of the 
knob, k, and immediately produce a clear 
homogeneous yellow light. The chimney, h, 
rests on the movable support,/, and ensures 
as steady a flame as possible. The lamp is so 
placed that the round opening, c, in the chim- 
ney, stands exactly in front of the opening, 
J), so that the field is illuminated perfectly 
symmetrically. In order to obtain the best 
possible results and at the same time to tire the eye least, it is 
well to place the apparatus in a dark room and carefully avoid 
every disturbing side light. 

When Ave have a sufficiently bright and perfectly homoge- 
neous light, about the mark 300 of the division, marking in grams, 
is brought into the field of the telescope, P, by turning the 




* The meclianicians, Hermann and Pfister, in Bern, who furnish Wild's Po- 
lar! strobometer of excellent finish at a price of about 300 marks ($75), have 
lately made instruments in which the circle is divided throughout in -\ degrees 
(360"), so that it is possible to read off the angle of rotation in all four quad- 
rants. 



18 




274 ANALYSIS OF THE URmE. 

knob, (7, and on looking through the polariscope, A, a bright- 
yellow field is obtained, which is traversed by horizontal black 
Fig. 33 a and h. lilies, and shows also the cross-hairs (fig. 33, a). 
If the latter do not appear sharply defined, 
the ocular of the telescope. A, is drawn out 
more or less, until they become so ; and now the 
horizontal black fringe will be most distinctly 
seen also. 

If we now turn the knob, (7, again (in the di- 
rection of the arrow) the horizontal lines grad- 
ually become paler and at last wholly disap- 
pear. This point in Wild's apparatus shows 
that the instrument is adjusted, just as in 
Soleil's saccharimeter the same color of the 
two quartz halves indicates the same thing. 
If the instrument is accurately adjusted, when the lines com- 
pletely disappear, the index mark exactly corresponds with the 
zero-point of the circle division. If a slight deviation should 
appear here, its amount may either be taken into account by 
addition or subtraction in later measurements, or with the aid 
of the two correction-screws, at G, the polariscope may be 
turned in its sheath, Z, micrometrically to the left, until the 
horizontal lines completely disappear, while the index line re- 
mains at zero. (Fig. 33, h.) 

Procedure in Estimating. According as the color of the per- 
fectly clear filtered urine is lighter or darker, the observing 
tube 100 or 200 mm. long is chosen for the estimation. We 
first bring the circle division, which is furnished with numbers 
running from to 100 and divided into \ degrees, into the field 
of the telescope, and adjust it exactly at the disappearance of 
the fringe, when about the division 50 will coincide with the 
index. Beading off the position is accomplished by estimating 
the tenth of a division at ^V°j when by multiplying by two the 
\° and the 3^0° are changed to jV° ^^^ tito °) so that we can write 
them as decimals. 

After the starting-point has been determined the tube filled 
with urine is placed on the apparatus and we turn toward the 
increasing numbers until the fringes disappear again. If the 
first reading is subtracted from the new one, we obtain the 
angle of rotation cy, from which the amount of sugar C, that is. 



QUANTITATIVE ESTIMATIONS. 



275 



the weight of diabetic sugar present in a liter, is giren in grams 
by means of the formula 

= 1773 — 
L 

in which 1773 is the constant rotation of diabetic sugar ac- 
cording to Hoppe-Seyler's most recent determinations,* L the 
length of the tube in millimeters, and a represents the angle of 
rotation observed. 

The following table gives the results of these calculations 
for whole degrees and tubes 100 and 200 mm. long : 



AKGLE OF DEVIATION. 


100 MM. 


200 MM. 


1° 


17-73 


8-865 


2° 


35-46 


17-730 


3° 


5349 


26-595 


4° 


70-92 


35-460 


5° 


88-65 


44-325 


6° 


106-38 


53-190 


7° 


12411 


62-055 


8° 


141-84 


70-920 


9° 


159-57 


79-785 


10° 


177-30 


88-650 



Example : 

When the tube is empty or removed, we have found 50° as the 
point of departure. After filling the tube 100 mm. long with urine 
the adjustment with homogeneous sodium light gave 53-61°; the 
angle of rotation, therefore, is 3*61°^ and from it we can reckon for 
the observation tube 100 mm. long according to the above table : 

As concentration for 3°, 53-190 grm. 

As yV of the concentration for 6°, . . . .10-638 '' 
As yj^ of the concentration for 1°, .... 0-177 *' 



Amount, 64-005 grm. 



f Zeitschrift f. analyt. Cliem., Band 14, Heft 3. 



276 



AI^ALTSIS OF THE URINE, 



In one liter of urine, therefore, there are contained 64*005 
grm. of diabetic sugar. 



4. ESTBIATION OF SUGAR BY FERMENTATION. 

A. Principle, From § 25, D, 8, we know that diabetic sugar 
mixed with yeast undergoes vinous fermentation. One equiva- 
lent of diabetic sugar thereby decomposes into 2 equivalents 
of alcohol and 4 equivalents of carbonic acid ; if we esti- 
mate the carbonic acid formed by the fermentation of a fixed 
amount of diabetic urine, we can calculate from it the quantity 
of sugar present. 100 j)arts of carbonic acid correspond to 
204-54 parts of sugar. 

B. Performance. In carrying out the test we use the appara- 
tus represented in fig. 34. 20 or 30 cc. of urine are placed in the 
small flask A, a little well-washed so-called dry yeast and a small 
amount of tartaric acid are added, and it is connected by means 
of the bent tube c with the small flask B, which is half filled with 
concentrated sulphuric acid. The tube a of the small flask A is 
closed at the top by a little ball of wax, h, and the apparatus is 
then weighed. It is next exposed to a temjDerature of about 30° 
or 40^ C, when fermentation with the evolution of carbonic acid 
will commence directly. The bubbles of gas pass through the 
tube c and the sulphuric acid in the flask B, and then escape 
perfectly dry through the tube d, which should be connected 

with a small U-shaped chloride of 
calcium tube, so as to prevent the 
access of atmospheric moisture to 
the concentrated sulphuric acid in B. 
In most cases the fermentation is 
completed in two or three days, the 
evolution of carbonic acid then ceases, 
and all of the sugar is decomposed. 
Then after gently warming the flask 
A to remove the carbonic acid which 
is still retained, a little air is drawn 
through the apparatus at the tube 
a until there is no longer any taste 
of carbonic acid, and it is then 
weighed again. The loss of weight gives us directly the amount 



Fig. 34. 




QUANTITATIVE ESTIMATIONS. 277 

of carbonic acid formed by tlie decomposition, and from this we 
can easily calculate tlie corresponding amount of sugar, since 
48*89 parts of carbonic acid correspond to exactly 100 parts of 
diabetic sugar. 

If the urine contains albumen it must be coagulated by boil- 
ing, since otherwise decomposition may readily occur, which, as 
is well known, is accompanied by the evolution of gas. By the 
addition of tartaric acid, according to Lehmann, other decom- 
positions are prevented, while at the same time the vinous fer- 
mentation is promoted. 

From the experiments of Pasteur there is no longer any doubt 
that in the fermentation of sugar, not only carbonic acid and 
alcohol, but also other substances, amyl alcohol, butyl alcohol, 
etc., and even succinic acid and glycerine, may be formed, so 
that the carbonic acid is not a perfectly accurate measure of the 
sugar ; this may be the reason why many chemists have always 
found less sugar in diabetic urine by the fermentation test than 
by the excellent method of Fehling. I unconditionally prefer 
Fehling's method. 

5. Quantitative Estimation of Sugae feom the Difference 
IN Specific Gravity before and after Fermentation. 

The method proposed by Eoberts, in the year 1861, of esti- 
mating the sugar in the urine from the difference in specific 
gravity before and after fermentation, has recently been sub- 
jected to a rigid test by Manassein,* who has established the 
usefulness of the procedure beyond all doubt. 

After the specific gravity of the original urine has been deter- 
mined by the picnometer or a delicate Mohr balance, with care- 
ful consideration of temperature, it is treated with pure washed 
yeast and left to ferment in a sufficiently large flask, best at a 
temperature of from 20° to 24° C. At the temperature above 
given the fermentation is usually ended in twenty-four hours ; 
the fluid now becomes clear and the yeast settles to the bottom. 
When this point is reached it is filtered, and the specific gravity 
of the clear fluid is once more determined with the picnometer 
or the MohT balance. 

* Centralblatt f. d. med. Wissenscliaf t. , 1872, p. 551. 



278 ANALYSIS OF THE URINE. 

For a difference of 0*001 in the specific gravity before and 
after fermentation we reckon 0*219 percent, of sugar. If a urine 
before fermentation, therefore, had a specific gravity of 1*0298, 
and after it one of 1*0055, the amount of sugar would be calcu- 
lated for the difference of 0*0243 at 

0-0243 X 0-219 ^ .,^ 

CRm =5*32 per cent. 

Or the difference of the specific gravities is multiplied by 1000 
and divided by the factor 4-56, which would be obtained by 
multiplying the difference of the specific gravities by 1000 and 
dividing this product by the per cent, of sugar found with the 
polarizer. According to this the amount of sugar for a differ- 
ence in the specific gravities of 0*0243 is reckoned at 

0-0243x1000 . „,. , 
-—— =5-33 per cent. 

4-OD 

From a number of estimates which I have made the above 
method is by no means inferior in point of accuracy to others. 
That it requires at least twenty-four hours time and that yeast 
is not always at hand in the laboratory are disadvantages which 
it has in common with the methods hitherto used for estimating 
the sugar by fermentation. 

§71. 

1. Estimation of Iodine by the Method of Kersting."^ 

A. Principle, The method of estimating iodine depends 
simply on the fact that all of the iodine is separated from even 
a tolerably dilute solution of a metallic iodide by distillation 
with sulphuric acid, so that no more traces of iodine can be 
detected in the residue if the distillation is continued suffi- 
ciently long. The iodine is estimated in the distillate by a 
standard solution of chloride of palladium. If a solution of a 
metallic iodide is mixed with an excess of a solution of the 
chloride of palladium and a little hydrochloric acid at from 60° 
to 100°, the iodide of palladium formed separates on shaking 
after a few seconds in black caseous flakes and the supernatant 
fluid appears perfectly clear and colorless. If, on the other 

*Aniial. d. Chem. u. Pharm., Band 87, p. 21. 



QUANTITATIVE ESTIMATION'S. 279 

hand, the iodide solution is present in excess, the precipitation 
takes place much more slowly and the palladium iodide deposits 
partly on the sides of the glass as a black coating. For these 
reasons, therefore, in the estimation of iodine we do not add the 
solution of palladium to that of the iodine, but we measure off a 
fixed volume of the latter and determine the amount of the 
fluid to be tested for iodine which is just sufficient to precipi- 
tate a definite amount of palladium solution. Since the mixture 
becomes almost absolutely clear on heating and shaking, and 
since in the second place 3V to -^^^-^j mgrm. of iodine may be 
detected by palladium, and conversely jo o^otto^ mgrm. of palla- 
dium may be distinctly recognized by means of iodine by the 
occurrence of a brown color, the estimations appear to be very 
accurate according to my own experiments performed with pure 
solutions of iodide of potassium and palladium chloride, both of 
known strength. 

B. Preparation of the Solutions, 

1. Standard Solution of Iodide of Potassium. 

The solution of iodide of potassium must contain exactly yoV o" 
of iodine, and is, therefore, readily obtained by weighing off 
1'308 grm. of pure ignited iodide of potassium, free from iodate 
of potassium, dissolving and diluting it to a liter. 1 cc. of this 
solution contains then 1 mgrm. of iodine, since 1*308 grm. of 
iodide of potassium exactly correspond to 1 grm. of iodine 
(127: 166-11 = 1: ^=1-308). 

This solution of iodine is used for standardizing the solution 
of chloride of palladium. 

2. Acid Solution of Chloride of Palladium, 

a. Dissolving the Palladium. 

The palladium solution is prepared from the metal. For 
example, 1 grm. is weighed off, dissolved in hot aqua regia, 
evaporated to dryness at 100°, then fifty parts of concentrated 
hydrochloric acid are added and diluted with water to 2,000 cc. 
Since, however, commercial palladium is probably seldom pure, 
the true strength of this solution must be ascertained, for which 
purpose the iodide of potassium solution 1 may be used, which 
contains -y^j^-q of iodine. 

b. Titration of the Palladium Solution, 

10 cc. of the palladium solution to be tested are put into a 
small flask of about 100 or 200 cc. capacity, the glass is stop- 



280 ANALYSIS OF THE URINE. 

pered, and heated' on the water bath to 60° or 100°. The iodine 
solution 1 is now gradually added from a pipette or burette, it 
is vigorously shaken and heated a few seconds. A small amount 
of the fluid, which becomes clear in a few minutes, is poured 
into two small, narrow test tubes, so that both contain about 
one or two inches of fluid. A few drops of the iodine solution 
are then added to one tube and compared with the other to see 
whether a brown color is produced or not. If the former is 
the case, the specimens are washed into the original fluid, more 
iodine solution is added, it is shaken, heated, again tested in 
the manner indicated, and the process continued until a new 
amount of iodine produces no further color. When this point 
is attained a little fluid is filtered off", and if it is not perceptibly 
browned either by palladium or by the iodine solution, it can con- 
tain scarcely t(7o o otto of an excess of these substances. Although 
this process appears difficult and tedious, it may be easily and 
accurately performed in at most ten minutes. We calculate the 
amount of palladium in the solution of palladium chloride from 
the number of cc. of the iodine solution used. 

1 cc. of the iodine solution contains 1 mgrm. of iodine, and 
this corresponds to 042 mgrm. of palladium (127: 53*3 = 1: a; 
-0-42). 

For example, if we have used 11*9 cc. of the iodine solution 
to precipitate 10 cc. of the palladium solution, they correspond, 
since they contain exactly 11*9 mgrm. of iodine, to 11*9 x 0*42 
mgrm. of palladium. 10 cc. of the palladium solution con- 
tain, therefore, 4*998 mgrm. of palladium, and require of an 
iodine solution of unknown strength a volume in which exactly 
11*9 mgrm. of iodine are contained, from which the amount of 
iodine in the whole fluid may be readily calculated. 

C. Performance of the Analysis with Urine. 

In order to determine the amount of iodine present in urine 
which contains it, it is first necessary to separate it by distilling 
with sulphuric acid. The distilling apparatus represented in 
fig. 35 may be used for this purpose : « is a flask of about 300 
cc. capacity, it is connected by a bent glass tube with the Lie- 
big's condenser, cc, in which the vapors are condensed, and the 
distillate is collected in the small glass d, which serves as a re- 
ceiver. If the quantity of iodine in the urine is at all consid- 
erable, 50 or 100 cc. are measured off with a pipette into the 



q UANTITA TIVE E8T1MA TI0N8. 



281 



Fig. 35. 




flask a, whicli is placed in cold water, and then, while carefully 

avoiding too great a heat, 20 cc. of concentrated chemically 

pure (particularly that which is free from iodine) sulphuric 

acid is added drop by drop. 

The flask is then connected 

with the condenser and the 

fluid is distilled until white 

fumes of sulphuric acid 

appear in the neck. If the 

urine contains but little 

iodine, however, a measured 

amount, about 200 or 250 cc, 

is supersaturated with liquor 

potassii, and distilled until 

from 20 to 40 cc. remain. 

This distillate contains no 

iodine. Observing the pre- ^ 

caution given above, 20 cc. of 

concentrated sulphuric acid are then poured on to the cooled 

residue in the flask, and the distillation is completed as before, 

that is, until the sulphuric acid begins to vaporize. 

The distillate thus obtained in both cases contains hydriodic 
acid, all of the volatile acids of the urine, carlDonic acid, sul- 
phurous and sulphuric acids. Before it can be used for esti- 
mating the iodine, the sulphurous acid must be oxidized and 
removed. This is readily accomplished as follows : The distil- 
late obtained is treated with one or two drops of starch paste 
(one part of starch, ^^ of sulphuric acid, and twenty-four parts 
of water), then a saturated solution of calcic hypochlorite is 
dropped into it until the fluid just begins to become blue, and 
the blue color is again driven away by one or two drops of 
weak sulphurous acid water. The distillate is now ready for 
estimating the iodine ; after the whole volume has been deter- 
mined, which, therefore, corresponds to the amount of urine 
taken, it is poured into a Mohr's pipette, exactly 10 cc. of the 
standard solution of palladium are measured off, put into a 
glass, heated on the water bath, the urine-distillate containing 
iodine is then added, and the analysis performed exactly as be- 
fore, according to B, 2, b. 

If, for example, we have obtained 96 cc. of distillate from 



282 ANALYSIS OF THE URINE. 

100 cc. of urine, and have used 12 cc. of it to completely pre- 
cipitate the 10 cc. of palladium solution which contains 4*998 
mgrm., these 12 cc. contain 11*9 mgrm. of iodine (53 '3 : 127 
= 4-998 : x). (See B, 2, b.) 

In the 96 cc. of distillate, therefore, corresponding to 100 cc. 
of urine, there are 8 x 11*9 = 95*2 mgrm. of iodine (0*0952 grm.). 

2. Hilger's Method. 

While Kersting always obtained excellent results with the 
method described, Hilger* states that according to his experi- 
ments Kersting's method constantly yields too small results. 
Hilger, therefore, recommends the following as the simplest 
method for estimating iodine quantitatively : 

10 or 20 cc. of the palladium solution, according to the amount 
of iodine present in the urine to be tested, which is easily 
approximately determined by a qualitative test for iodine, are 
heated on the water bath in a glass vessel with a ground-glass 
stopper, and the urine containing iodine, first acidulated with 
hydrochloric acid and brought to a fixed volume, is added until 
all of the palladium is separated as iodide. The separation is 
very much hastened by violently shaking the mixture. Small 
amounts filtered off from time to time and treated with a few 
drops of the urine, on being heated indicate by becoming cloudy 
or remaining clear whether the reaction is finished or not. 
According to Hilger's observations the end of the reaction co- 
incides with the moment at which the separation of the iodide 
of palladium in distinct flocculi commences, when the fluid is 
kept constantly boiling. 

According to numerous experiments carried out by Hilger, 
the urine to be examined can, therefore, be directly used for 
estimating the iodine after it has been previously acidulated 
with hydrochloric acid. He also states that the removal of 
sulphuric acid, phosphoric acid, and other constituents of the 
urine is not necessary before performing the analysis. 

* Zeitschrift f. analyt Chem., Band 12, p. 342, u. Band 13, p. 475. 



QUANTITATIVE ESTIMATIONS. 283 

3. colorimeteic estimation of lodine by the method of h. 

Struve.* 

A. Principle, If a solution of iodide of potassium of known 
strength is prepared, and equal amounts of bisulphide of car- 
bon are added to different quantities of the solution, and then 
a few drops of red fuming nitric acid are added, it is well known 
that all of the iodine is set free, and, after shaking, is taken up 
by the bisulphide of carbon. A scale of colored fluids contain- 
ing known amounts of iodine is thus obtained, with which the 
shades of color obtained in the estimation of iodine in the urine 
are compared. 

B. Preparation of the Color Scale. Struve used a solution of 
1 grm. of iodide of potassium in 1,000 cc. of water : 1 cc. of 
it, therefore, contains O'OOl grm. KI or 0*00076 grm. of iodine. 
The burette used was such that 21 drops from it corre- 
sponded to 1 cc. 5 cc. of bisulphide of carbon are used with 
each test. If, then, the iodine is set free by a few drops of 
fuming nitric acid, and by shaking transferred to the bisul- 
phide of carbon, the acid is removed by. decanting with dis- 
tilled water, and we thus obtain under a layer of pure water 
equal quantities of bisulphide of carbon, which are colored 
by different but definite quantities of iodine. All of these 
normal solutions, under a thin layer of water, are then sealed 
in glass tubes of pure white glass, which have a length of 15 cm. 
and an internal diameter of 8 mm. If the tubes are absolutely 
clean, more especially if they are free from organic matters, 
they retain the different shades of color for a long time without 
marked change if they are protected from direct sunlight and 
if the tubes are preserved in a cool, dark place. 

In estimating iodine in the urine, the colored bisulphide of 
carbon which results is poured into a tube, which has the same 
dimensions as those containing the normal solutions, and the 
color is compared with the scale, which is best accomplished 
on a background of white paper with reflected light. 

* Joum. f. pr. Chem., Band 105, p. 429. Zeitschrift f. analyt. Chem., Band 8, 
p. 280. 



284 ANALYSIS OF THE TJBINE. 

Struve used the following scale : 



KUMBEE OF DROPS OF 






THE IfORMAL 


KI 


IODIDE OF POTASSIUM. 


lODIKE. 


SOLUTION. 








1 




0-000048 


0-000036 


2 




0-000096 


0-000072 


3 




0-000144 


0-000108 


4 




0-000192 


0-000144 


6 




0-000288 


0-000216 


8 




0-000384 


0-000288 


10 




0-000480 


0-000360 


12 




0-000576 


0-000432 


14 




0-000672 


0-000504 


18 




0-000864 


0-000648 


21 




0-001000 


0-000756 


30 




0-001440 


0-001080 



C. Performance. 20 cc. of water as cold as possible are poured 
into a pyriform flask of 50 cc. capacity and provided with a 
tightly fitting glass stopper; 1 cc. of the urine to be examined 
is then added, and afterward 5 cc. of bisulphide of carbon. 
The contents is gently shaken, and then a few drops of fum- 
ing nitric acid are added to the mixture from a small pipette. 
If it is now shaken and then left at rest, the bisulphide of 
carbon quickly collects on the bottom. The stopper is care- 
fully raised, the glass filled with water as cold as possible, 
it is shaken, allowed to settle, and the acid water drawn off 
with a small siphon. The bisulphide of carbon is thus washed 
two or three times with water, when the colored bisulphide 
of carbon may be poured into a small previously-prepared 
glass tube for the comparison. But, if it has been necessary 
to use a large quantity of urine for the experiment, for exam- 
ple, 10 or 100 cc, it must first be evaporated nearly to dry- 
ness on the water bath after the addition of potassic hydrate, 
a concentrated solution of chloride of ammonium must be 
added to the dark-brown residue, and the whole heated until 
the fluid has a neutral reaction and no longer smells of am- 



. QUANTITATIVE ESTIMATIONS. 285 

monia. When this point is reached, the cooled fluid is put 
into a flask, and the separation and estimation of the iodine 
carried out as indicated above. If, however, the bisulphide of 
carbon should not separate as a coherent mass, which indeed 
would scarcely happen, it is only necessary to evaporate the 
fixed volume of urine to dryness on the water bath, after add- 
ing the potassic hydrate, ignite the residue, extract with water, 
and test the filtered solution thus obtained, as recommended 
above, after it has been neutralized by boiling with chloride of 
ammonium. 

§ 72. Estimation of Ieon. 

A. Principle, If a solution of permanganate of potassium is 
added to the solution of a ferrous salt which contains an excess 
of hydrochloric acid, the ferrous oxide becomes oxidized, and 
the permanganate of potassium, on the other hand, is reduced 
to manganous chloride. One equivalent of permanganate of 
potassium (KO,Mn^O,) yields five equivalents of oxygen, and 
thereby converts ten equivalents of ferrous oxide to ferric. If 
now the strength of the permanganate of potassium solution is 
known, an unknown amount of iroUj which, of course, must be 
in solution as ferrous oxide, can be easily determined by ascer- 
taining the volume which is just sufficient to complete the oxi- 
dation. The end point of the experiment is very beautifully 
and distinctly shown, by the bright-red color which is imparted 
to the whole fluid by the first drop of permanganate of potas- 
sium solution in excess. 

B. Preparation of the Solutions. 

1. Solution of Permanganate of Potassium. 

This is prepared by dissolving chemically pure permanga- 
nate of potassium in distilled water. 

The strength of the permanganate of potassium solution 
must be determined anew before each series of experiments, 
since it gradually changes even with the most careful preserva- 
tion. This estimation is performed in the most simple manner 
with a solution of ferrocyanide of potassium, ten equivalents of 
which are changed by one equivalent of permanganic acid into 
five equivalents of ferricyanide of potassium. One equivalent 
of ferrocyanide of potassium (211*2) corresponds to one equiva- 
lent of Fe (28.) 



286 ANALYSIS OF THE URINE, 

2. Solution of Ferrocyanide of Potassium. 

7*543 grm. of perfectly pure, dry, crystallized ferrocyanide of 
potassium, corresponding to 1 grm. of iron, are dissolved in 
water and the solution diluted to a liter. 10 cc. of this solu- 
tion then correspond to exactly O'OIO grm. of iron. The solu- 
tion is to be kept in a well-stopped bottle. 

Titration of the Permanganate of Potassium Solution, 

100 cc. of the ferrocyanide of potassium solution (correspond- 
ing to 10 mgrm. of iron) are measured off with a pipette, di- 
luted with about 50 cc. of water, acidulated with hydrochloric 
acid, the vessel placed on a piece of white paper, and the dilute 
solution of permanganate of potassium dropped into it with 
constant stirring until the .occurrence of a reddish-yellow color 
in the fluid indicates that the conversion has been completed. 
Supposing we have used up to this point 20 cc. of permanga- 
nate of potassium solution, 1 cc. will, therefore, correspond 
to ^jf J-^ = 0*5 mgrm. of iron. A second experiment must estab- 
lish the accuracy. An oxalic acid solution which contains 1'125 
grm. of crystallized oxalic acid in the liter, corresponding to 1 
grm. of iron, may be used for the same purpose. In testing, 
10 cc. of this solution, corresponding to O'OIO grm. of iron, are 
heated almost to boiling, a little dilute sulphuric acid is added, 
and it is titrated with the permanganate of potassium solution 
until it becomes red. The volume used up to this point cor- 
responds to O'OIO grm. of iron. I prefer the latter method. 

C. Performance. In order to ascertain the amount of iron in 
the urine by this method, it is necessary to evaporate it and 
ignite the organic matters. 100 cc. of urine, therefore, are 
evaporated to dryness in a platinum dish and the ash is ob- 
tained exactly according to § 60. After cooling, the saline 
mass is dissolved in hydrochloric acid, heated, water is added, 
and the solution is carefully transferred to a flask of 100 or 
150 cc. capacity. Before the titration can be undertaken, the 
iron present as oxide must be reduced; a little sulphite of 
sodium is, therefore, added to the hydrochloric acid solution, 
and it is boiled until the fluid has become colorless and no 
more trace of sulphurous acid can be detected. When we 
have established the strength of the permanganate of potas- 
sium solution by means of the oxalic acid or ferrocyanide of 
potassium, the solution of iron is diluted to about 60 cc. ; it 



QUANTITATIVE ESTIMATIONS. 287 

is allowed to become completely cool, the glass is placed on a 
piece of white paper, and the permanganate of potassium solu- 
tion is dropped into it with constant stirring, until the fluid has 
assumed a faint rose-red color. Granted that 1 cc. of our so- 
lution of permanganate of potassium corresponded to 0*0005 
grm. of iron, and that we have used 3 cc. up to the commence- 
ment of the end reaction, the 100 cc. of urine, therefore, con- 
tained 3 X 0*5 mgrm. of iron = 0'0015 grm. The amount of iron 
found, multiplied by 1*43 gives the corresponding amount of 
ferric oxide; multiplied by 1'286 it gives the corresponding 
amount of ferrous oxide. 

The method is a good one, and gives accurate results. It 
must be remembered that the red color produced by the last 
drop disappears after a time, and we must not allow it to lead 
us into error. 

§ 73. Estimation of Ukic Acm. 

1. By Precipitating with Hydrochloric Acid. 

200 cc. of urine are put into a small beaker, 5 cc. of pure 
hydrochloric acid (sp. gr. = l'll) are added and the mixture 
thoroughly stirred with a glass rod ; the beaker is then covered 
with a glass plate and allowed to stand at rest in a cool place 
with the temperature as low as possible for twenty-four or 
thirty-six hours. At the end of this time the uric acid will 
be found to have separated in crystals more or less colored, 
which are to be collected and washed on a weighed filter and 
subsequently dried. 

But since papes is a very hygroscopic material, the weight 
of a dried filter cannot be determined directly. In this case, 
therefore, as in all others where bodies are to be collected on 
weighed filters and estimated, we make use of a simple con- 
trivance and one which at the same time answers all require- 
ments. Two watch glasses which are ground on the edge and 
therefore fit each other with perfect accuracy (fig. 36, hh) are 
selected ; these are held together by a brass clamp aa, so that 
the filter c lying between them is hermetically sealed. In dry- 
ing, the two watch glasses are placed one within the other, and 
with the filter lying on them are placed in the desiccator, fig. 
15. When the latter has been heated for a long time to 100°, 




288 ANALYSIS OF THE URINE, 

the watch glasses are placed together, the clamp is slid over 
them, and, after cooling over sulphuric acid, fig. 16, they are 

weighed. 

The uric acid separated 
is collected on the filter 
thus dried, first by washing 
those crystals which are 
on the surface of the fluid 
on to it, when the rest of 
the urine, which in most cases is clear, can be poured off, or, 
more safely, drawn off with a siphon, and then the uric acid 
which adheres to the walls and bottom of the glass is loosened 
with a feather with only a little of its beard left, or, better still, 
by a glass rod which has a small piece of rubber tubing drawn 
over its end, and transferred to the filter. For rinsing the glass 
and washing down the uric acid the filtrate first obtained, 
which is already saturated with uric acid, should be used, never 
water, since this would dissolve no inconsiderable amounts of 
the separated uric acid. When at last all of the uric acid is on 
the filter and the acid urinary fluid has run off even to the last 
drop, we begin to wash with cold water until the filtrate is 
no longer rendered cloudy by a solution of nitrate of silver. 
Large amounts of water must be avoided on account of the solu- 
bility of the uric acid. If only a small filter, having a radius of 
1 to 1^ inch, is used, then 30 cc. of water are quite sufficient for 
the most com]3lete washing in most cases. When this point is 
reached, the filter is taken from the funnel, laid on one of the 
watch glasses and dried for a long time in the air bath at 100°. 
The uric acid is then weighed exactly as before, fig. 36. What 
the apparatus has gained in weight is the rric acid which was 
contained in 200 cc. of urine. 

This simple method has two sources of error. First, a certain 
amount of uric acid always remains in solution, and second, the 
uric acid separated always carries down a little coloring matter 
with it. However, if we accurately observe the above condi- 
tions and use a filter of 1 to \\ inch radius which has first been 
thoroughly washed with hydrochloric acid and then with water 
before drying and weighing, the two sources of error mentioned 
above nearly counterbalance each other if only 30 cc. of water 
have been used in washing the uric acid. (Heintz.) This amount 



QUANTITATIVE ESTIMATIONS. ' 289 

of water will suffice in most cases, so tliat no further reaction 
can be obtained in tlie filtrate with nitrate of silver ; but if for 
any reason a larger amount of wash Avater should be necessary, 
the two errors mentioned would no longer mutually cancel each 
other ; that caused by the solubility of the uric acid would pre- 
dominate, and, in order to counterbalance it, we must add 0*045 
mgrm. to the amount of uric acid found by weighing for every 
cubic centimeter more than 30 of wash water which has been 
used. If, for example, the wash water amounts to 70 cc, we 
must add 40 x 0*045 mgrm. to the amount of uric acid found by 
weighing. 

If a urine in which we wish to estimate the uric acid contains 
albumen, we use the filtrate from the albumen coagulum which 
corresponds to a known volume of urine, and proceed with it as 
recommended above. 

Numerous methods have been proposed for estimating the 
uric acid volume trically, but all have proved unsuitable or 
wholly unserviceable. Permanganic acid certainly has a very 
energetic action on uric acid, but we cannot titrate it with per- 
manganate of potassium directly in the urine, since many other 
substances are also destroyed by this energetic oxidizing sub- 
stance. There is nothing left but to first precipitate the uric 
acid by an acid, filter, wash, dissolve in potassic hydrate, and 
titrate the solution with permanganate after acidulating. It 
would probably be simpler and more accurate under these cir- 
cumstances, however, to weigh the washed and dried uric acid 
directly. The proposition to estimate the uric acid volumetri- 
cally by a solution of iodine in iodide of potassium has proved 
wholly impracticable.'^ 

Naunyn and Riess t lay stress on the fact that in the estima- 
tion of uric acid in diabetic urine the usual method of precipi- 
tating with hydrochloric acid, etc., does not suffice ; they there- 
fore precipitate the urine with acetate of mercury, decompose 
the precipitate with sulphuretted hydrogen, and determine the 
uric acid in the filtrate obtained. 



*Zeitschrift f. analyt. Chem., Band 7, p. 516. 

t Centralbl. f. d. med. Wissensch., 1870, p. 567. Zeitschr. f. analyt. Chem., 
Band 9, p. 538. 
19 



290 AJ^ALYSIS OF THE URINE. 

2. Estimation of Uric Acid by Scdlwivskis llethod. 

Salkowski"^" and Malyt have proved that all of the uric acid 
is not precipitated from the urine by hydrochloric acid, but that 
under certain circumstances considerable amounts remain in 
solution and can be precipitated from the filtrate as urate of 
magnesium and silver and can be determined quantitatively. 

The method given by Salkowski for this purpose is the follow- 
ing : After the uric acid, precipitable by hydrochloric acid, has 
been filtered off and washed, the filtrate is neutralized with 
ammonia and precipitated wdth a strong magnesia mixture con- 
taining ammonia. Since by this, under certain circumstances 
and on long standing, urate of magnesium sej)arates, it is filtered 
immediately, washed, and the filtrate and wash water treated 
with an ammoniacal solution of nitrate of silver in excess. The 
precipitate which results is filtered off preferably with the aid 
of the Bunsen pump, and washed until the wash water not only 
remains clear on acidifying, but also no longer gives any chlo- 
rine reaction on the addition of nitrate of silver. The precipi- 
tate is then washed into a flask, distributed by continued and 
energetic shaking, and decomposed by sulphuretted hydrogen, 
for which a somewhat long exposure is necessary. The fluid 
with the precipitate is then heated for a time, filtered, the filtrate 
evaporated to a small volume, strongly acidified with hydro- 
chloric acid, and left at rest thirty-six or forty-eight hours. The 
uric acid thus obtained is collected on a small weighed filter, 
washed, dried, and weighed ; it is pure with the exception of 
imponderable traces of sulphur. 

Schwanert, J however, is of the opinion that the amount of uric 
acid which remains in solution after precipitation with hydro- 
chloric acid maybe readily determined by the ratio of solubility 
of uric acid in mixtures of hydrochloric acid and urine, as given 
by Yoit and Zabelin § and substantiated by Schwanert, so that 
the above-described somewhat detailed method is superfluous. 
According to Yoit, Zabelin, and Schwanert, in every 100 cc. of 
the hydrochloric urinary fluid 0*0048 grm. of uric acid remain 
in solution, which must be added to that found directly. 

*Zeitschrift f. analyt. Chem., Band 11, p. 234. 

f Jahresbericlit ii. d. Fortscliritte d. Tliierchcmie, Band 2, p. 178. 

JAnnal. d. Cliem. u. Pliarm., Band 163, p. 153. 

§ Annal, d. Chem. u. Pliarm. , Suppl. Band 2, p. 313. 



QUANTITATIVE ESTIMATIONS. 291 

In proof of Lis assertion Scliwanert quotes fifteen compara- 
tive analyses in which the nric acid was determined according 
to Salkowski's method, and the amount obtained compared with 
that which remained dissolved in the fluid which was used, and 
reckoned at 0*0048 grm. for each 100 cc. 

According to these fifteen double analyses the amount of uric 
acid which can be precijDitated by hydrochloric acid and the 
solution of nitrate of silver is almost exactly the same as the 
amount pre cipi table by hydrochloric acid alone plus 0"0048 grm. 
for each 100 cc. of the filtrate, etc. 

Salskowski ^ acknowledges these objections of Schwanert to 
his method, and grants that he by no means regards the esti- 
mation of uric acid by precipitation with nitrate of silver as a 
commendable method, but that there continues to be an urgent 
need of a still better procedure for estimating the uric acid. 
But if Salkowski considers the agreement of the numbers ob- 
tained by Schwanert by the silver precipitation with those cal- 
culated by using the correction as simply accidental, we cannot 
agree with him, since, with a concurrence in fifteen cases, there 
can scarcely be any question of simple chance. As for myself, 
I used only the correction given by Schwanert for the uric acid 
remaining in solution after treatment with hydrochloric acid. 



§ 74. Estimation or Kkeatinin. 

A. Principle, Kreatinin, as is known, gives with chloride of 
zinc a compound of kreatinin chloride of zinc (CgH^NaO.^ZnCl) 
quite readily soluble in hot water, and very insoluble in cold 
strong alcohol, which, according to my investigations, is emi- 
nently adapted for the gravimetric determination of this very 
important constituent of urine. 100 parts of kreatinin chloride 
of zinc correspond to 62*44 parts of kreatinin. 

One part of kreatinin chloride of zinc requires 9217 parts of 
alcohol of 98 per cent., and 5743 parts of alcohol of 87 per cent, 
to dissolve it. 

B. Preparation of tJie CMoride of Zinc Solution. Chemically 
pure oxide or carbonate of zinc is dissolved in pure hydrochlo- 
ric acid, and the solution evaporated on the water bath to a 

* Berichte d. d. chem. Gesellscliaft, Band 5, p. 410. 



292 AJSTALYSTS OF THE URINE. 

very tliick syrup, until all of the free liydrochloric acid is com- 
pletely removed. The cooled residue is dissolved in quite 
strong alcohol and the solution diluted to 1-20 specific gravity. 
C. P erf or malice. 200 or 300 cc. of urine collected within 
twenty-four hours, mixed together and accurately measured, are 
treated with a little milk of lime until the reaction becomes al- 
kaline, and a dilute solution of chloride of calcium is added as 
long as a precipitate results. After one or two hours it is fil- 
tered, filtrate and wash water are evaporated to a thick syrup 
on the water bath as quickly as possible, and, while still warm, 
are mixed with 40 or 50 cc. of alcohol of 95 per cent. The mass, 
thoroughly mixed, is put into a small beaker, the evaporating 
dish is rinsed with a small amount of alcohol, and it is left in a 
cool place six or eight hours for the complete separation of all 
that is precipitable. The fluid is then filtered through as small 
a filter as possible ; at last, when all of it has passed through, 
the precipitate is collected on the filter and washed with a small 
amount of alcohol. If the whole filtrate amounts to much more 
than 60 cc. it is allowed to evaporate on a hot iron plate to 50 
or 60 cc. When it has perfectly cooled, \ cc. of the alcoholic 
solution of chloride of zinc is added, it is stirred for a 
long time, which aids the se23aration very much indeed, and it 
is then allowed to stand two or three days in a cool place, 
covered with a glass plate. When this time has expired, the 
crystalline precipitate is collected on a dry weighed filter be- 
tween two watch glasses (fig. 36), making use always of the 
mother liquor for washing it on to the filter. When all of the 
kreatinin chloride of zinc has been collected on the filter and is 
completely freed from the mother liquor, it is washed with 
small quantities of alcohol until the latter passes through color- 
less and no longer reacts for chlorine. The washing should be 
thorough but not uselessly long. The filter, with the kreatinin 
chloride of zinc, is lastly dried at 100°, and weighed between 
the watch glasses. 100 parts of it correspond to 62*44 parts of 
kreatinin. The kreatinin chloride of zinc thus obtained is a 
faintly yellow-colored powder, which the microscope shows to 
consist of yellow transparent spheres of varying size, with 
sharp contours. According to my estimates this product con- 
tains about 94 per cent, of pure kreatinin chloride of zinc, but 
since the precipitation, on account of the solubility of this 



QUANTITATIVE ESTIMATIONS. 293 

body, is never absolutely complete, we can confidently regard 
it as pure, and for 100 j)arts of it reckon 62*44 parts of krea- 
tinin ; the two errors will then nearly counterbalance each 
other. But the alcoholic extract of the urinary residue must 
always be allowed to stand several hours, as specified, before it 
is filtered and the kreatinin precipitated, in order that every- 
thing precipitable, especially the chloride of sodium, shall have 
separated, since otherwise the kreatinin chloride of zinc is fre- 
quently mixed with cubes of chloride of sodium, which would 
render the entire estimation false. I therefore advise that the 
kreatinin chloride of zinc, after being weighed, should be mois- 
tened with absolute alcohol, and finally examined microscopi- 
cally; it must show the forms described in § 3, C, 1, and be 
absolutely free from cubes of chloride of sodium. 

This method gives satisfactory results. With pure kreatinin 

99 and 99-2 per cent, instead of 100 were found. (Analytical 
Experiments.) 

In diabetic urine the sugar must be destroyed before the 
kreatinin is determined. Of the daily amount of urine 500 or 
1,000 cc. are treated with fresh pure yeast and allowed to stand 
in a moderately warm place until the fermentation is complete. 
It is then precipitated with milk of lime and chloride of calcium 
as described, filtered, evaporated, and the residue extracted with 

100 cc. of alcohol of 95 per cent. After standing several hours 
the alcoholic solution is filtered off, evaporated to 50 cc, and 
after cooling precipitated with chloride of zinc solution as 
above. If the microscopic examination of the weighed kreatinin 
chloride of zinc should show admixture with foreign substances, 
a quantitative estimation of the zinc is made, and from this 
the kreatinin present is calculated. 100 parts by weight of 
kreatinin chloride of zinc correspond to 22 '4 parts by weight 
of zinc oxide. (Winogradoff and Gaethgens.)^ 

§ 75. Estimation of Albumen. 

A. Gravimetric. The quantitative estimation of albumen 
depends, as the qualitative recognition of it does, on its coagu- 
lation by heat, and that this may be complete, a most careful 
observance of the precautions given already in § 23 is required. 

* Zeitschrif t f. analyt. Cliem., Band 8, p. 100. 



294 ANALYSIS OF THE URINE. 

According to the greater or less quantity of albumen present 
20, 50, or 100 cc. of the urine previously filtered are put into a 
correspondingly large beaker with a pipette, so that we do not 
get more than 0*2 or 0*3 of coagulated albumen, by which the 
whole estimation is very much facilitated. With concentrated 
urines, moreover, it is well to dilute the urine before heating. 
If, therefore, when there is a large amount of albumen only 20 
cc. of urine are measured off, this is diluted with 80 cc. of water ; 
50 cc. of urine, with 50 cc. of water, etc. If, on the contrary, the 
amount of albumen is so small that 100 cc. of urine do not con- 
tain more than 0*2 or 0*3 grm. of albumen, a further dilution is 
not advisable. The beaker is then heated on the water bath 
for half an hour ; if there is not enough free acid present, if a 
coarse flocculent coagulation does not occur, and if the super- 
natant fluid does not become completely clear, one or two drops 
of acetic acid are added with a glass rod and the heat is con- 
tinued, Avhereupon a coarse flocculent coagulation of the albu- 
men does ensue and the fluid becomes clear. An excess of 
acetic acid must be avoided, since a part of the albumen dis- 
solves in the acid again if too much has been added, and would 
therefore escape calculation. But, on the other hand, the 
urine under no conditions should have an alkaline reaction, 
since a soluble alkaline albuminate, which does not coagulate 
at all on boiling, is formed. 

"We can treat the urine with acetic acid before heating, but in 
this case still more care is necessary, since, when too much 
acid has been added, coagulation does not take place on heat- 
ing. If the urine is acid, the addition of acetic acid is not really 
necessary, although the coarse flocculent and complete coagu- 
lation of the albumen is at all events very much expedited 
thereby. 

If the coagulation in thick flakes has been complete, the pre- 
cautions mentioned having been observed, and if the superna- 
tant fluid has become clear, filtration may be commenced. 

The fluid which stands above the coagulum is first poured on 
a dried folded filter, which has been weighed and moistened 
with water, this fluid runs through clear and quickly if the 
amount of albumen is not too large and the urine has been suf- 
ficiently diluted, so that the coagulation has been complete, 
when last of all the greater part of the coagulum is placed on 



QUANTITATIVE ESTIMATIONS. 295 

tlie filter. Wlien all of the fluid lias passed tlirougli, tlie albu- 
men is washed with hot water into the apex of the filter, which 
is easily accomplished. The beaker is now rinsed wdtli hot 
water, the last particles of albumen are loosened with a feather 
and the whole is thus collected on the filter, which is then 
washed with hot water until the filtrate no longer gives any re- 
action with nitrate of silver and on being ignited leaves no resi- 
due on platinum foil. If the operation is performed in the man- 
ner I have described above, the filtration takes place very well 
and very rapidly, otherwise it is often very slow and tedious. 

The filter is now carefully removed from the funnel, placed 
on one of the two watch glasses, fig. 36, and dried on the water 
bath at 100 "" until it no longer loses weight after cooling over 
sulphuric acid. Great care is to be exercised here, since the 
albumen, especially when we have too large an amount on the 
filter, usually cakes together into a horny mass, and, as it w^ere, 
becomes covered with a dry crust, while moisture is still con- 
tained within it and can only be removed by very slow drying 
at 100° (six or eight hours). Therefore the drying operation 
can only be regarded as completed Avhen two weighings agree, 
the filter having in the meantime been exposed to the given 
temperature for a considerable time. After deducting the 
weight of the watch glasses and of the filter from the Aveight 
last obtained, we obtain the quantity of albumen which was 
present, and which may then be calculated for the whole amount 
of urine. 

The estimation of albumen performed in this manner is sub- 
ject to two errors, for in the first place the albumen in its co- 
agulation carries down with it a little coloring matter, which 
cannot be removed even by prolonged washing with hot water. 
This is the reason why dried albumen in most cases appears to 
be yellow or even brown. However, this source of error is very 
inconsiderable and may be safely neglected. But frequently 
the earthy phosphates also separate with the albumen and 
naturally cause the amount of albumen to appear too great. 
In perfectly accurate estimations, therefore, the dried and 
weighed albumen, together with the filter, must be ignited in a 
weighed platinum crucible until all of the carbon has disap- 
peared, which can be easily accomplished in a short time when 
the crucible lies obliquely. The increase in weight of the pla- 



296 ANALYSIS OF THE URINE. 

tinum crucible minus tlie known weight of tlie filter asli gives 
the amount of ash of the weighed albumen, which must be sub- 
tracted from the amount of albumen first found. In most cases 
this roundabout way is unnecessary ; I have repeatedly satis- 
fied myself that the amount of ash in albumen coagulated from 
a sufficiently dilute acid urine is very small and consequently 
has a very slight influence on the result. 

20 cc. of a urine rich in albumen were diluted with 80 cc. of 
water, coagulated in a beaker on the water bath and the coagu- 
lum collected on a folded filter, thoroughly washed and dried at 
100° to a constant weight. The albumen weighed 0*3573 grm., 
which calculated for the whole twenty-four hours' amount of 
urine (1,050 cc.) = 18 '76 grm. After igniting and subtracting the 
filter ash there remained 0-0013 grm. of albumen ash. After 
subtracting this the twenty-four hours' amount of albumen was 
calculated at 18*69 grm. instead of 18*76 grm. first found. 

B. By Circumpolarization. If the amount of albumen in a 
urine is not very small, the urine itself not too dark colored, 
and if it becomes perfectly clear on being filtered, the albumen 
may be estimated also by means of the polarizing apparatus of 
Soleil-Yentzke. The method is exactly the same as was de- 
scribed in the estimation of sugar in § 70, 3. If the color and 
transparency of the urine permit, an observing tube 200 mm. 
long should be used, and after being carefully filled and placed 
in the apparatus, by turning the compensator the two halves of 
the field of the double plate are made exactly isochromatic. 
The zero-point of the nonius now lies on the left side of the 
zero-point of the scale, and each division with a tube 200 mm. 
long corresponds to 1 grm. of albumen in 100 cc. of urine ; and 
each division of the nonius to 0*1 grm. If, however, we have 
used a tube only 100 mm. long, the divisions of scale and nonius 
are to be multiplied by two in order to find the per cent, of 
albumen in 100 cc. of urine. If the urine does not become suf- 
ficiently clear by filtration alone, the turbidity may frequently 
be cleared up by a drop of acetic acid or a few drops of car- 
bonate of sodium or milk of lime without thereby changing the 
sj)ecific rotation of albumen. After filtration the urine is clear 
enough in most cases to allow of its examination in the po- 
larizing apparatus, in some cases, however, it fails. (Hoppe- 
Seyler.) 



QUANTITATIVE ESTIMATIONS. 297 

Since, as my abundant experience lias shown, the cases are 
very rare in which the method of determining albumen quanti- 
tatively described under A cannot be performed, I content my- 
self with merely mentioning here the other methods which have 
been proposed, for none of them equals in accuracy the gravi- 
metric, which, properly performed, gives the desired result 
quickly and accurately. 

1. The Metliod of Buleker'^ depends on the fact that albumen 
in an acetic acid solution is com^^letely precipitated by ferrocy- 
anide of potassium. This procedure gives only approximate 
results, of which I have convinced myself several times. Also 
Thomas t states that if the albumen does not amount to 1'5 or 
2 per cent., the results are Avholly unreliable. In all cases in 
w^hich the quantity of albumen was very small, Thomas found by 
Bodeker's method very much more albumen than by weighing. 

2. VocjeVs Optical 3Iethod.'\. The urine is rendered faintly acid 
with acetic acid, measured amounts of 4 or 6 cc, etc., are di- 
luted to 100 cc. with water, heated to boiling, quickly cooled 
and tested by ascertaining whether the light from a stearine 
candle is still perceptible through a layer of the mixture 6 '5 cm. 
thick. The experiment is repeated with different degrees of 
concentration until a dilution is reached at which the picture of 
the flame just disappears. The percentage of albumen in the 
urine is found by dividing the mean number 2'3553, obtained 
by Dragendorff by chemical analysis, by the number of cc. 
of urine used. Dragendorff performed thirty-five comparative 
analyses ; three times differences of more than 0"1 were shown, 
eleven times of more than 0*05, so that of thirty-five analyses 
twenty-one corresponded with the gravimetric method to with- 
in 0*05. Masing obtained in seven comparative analyses differ- 
ences up to 20 per cent., which were plus as well as minus. 

3. Lang, Haebler, snad Bornhardt^ calculate the amount of albu- 
men in the urine from the difference in the specific gravity of 
the urine before and after it has been coagulated by heating. 
According to Haebler this difference must be multiplied by 210, 

* Annal. d. Cliem. u. Pliarm., Band 111, p. 195. 
f Sclimidt's Jahrbliclier, Baud 120, p. 171. 

I Zcitsclirift f. analyt. Chemie, Band 7, p. 152. Masing, Beitrage zur Albiimi- 
ncmetrie, Dorpat, 1867. 
§ Zeitschrif t f. analyt. Chem., Band 7, p. 513, und Band 9, p. 149. 



298 Al^ALYSlS OF THE URINE. 

according to Bornhardt by 415, in order to find tlie percentage 
of albumen in the urine. My experiments show that Haebler's 
quotient is absolutely false, and also that Bornhardt's number 
yields with very careful manipulation only tolerable results when 
the amount of albumen in the urine is not too small, but with 
the low specific gravity of albumen and its small amount in 
the urine the limits of error are very great. Stscherlakoff and 
Chomjakoff " arrived at the same results. 

4. Melius lletJiod.f To 100 cc. of urine, which must not con- 
tain more than 0*2 to 0*4 albumen, 2 cc. of nitric acid are added, 
and then 10 cc. of a mixture of equal parts of crystallized car- 
bolic and glacial acetic acids with two parts of alcohol of 90 
per cent. It is filtered, first washed with water, to which J per 
cent, of carbolic acid has been added, and later with water con- 
taining alcohol, dried at 110^ C, and weighed. The carbolic 
acid precipitates the albumen without forming a chemical com- 
pound with it. 

According to examinations by Schaclit,:^ Mehu's method, 
especially in urines which contain a small amount of albumen, 
has no sort of advantage over the one described by me. 

5. 3IetJiod of P. Liborius.% 50 or 100 cc. of urine are treated 
in a beaker with four or five times its volume of alcohol of 85 
per cent. After twenty-four hours the coarse flocculent pre- 
cipitate is collected on a filter, washed, dried at 110° or 115° C. 
and weighed. The precipitate is then ignited in a weighed 
platinum crucible, the ash which remains, and is not inconsid- 
erable in quantity, is weighed, and its weight deducted from that 
first obtained. By this procedure Liborius always obtained 
more albumen than by coagulation or by the old method of 
Berzelius, which, moreover, yielded results agreeing with those 
obtained by coagulation. The reason of this is quite apparent, 
since alcohol not only precipitates albumen from the urine, but 
all albuminous bodies also, especially peptone, which, accord- 
ing to Senator, II is never absent from any albuminous urine, as 

" Zeitsclirif t f . analyt. Chem. , Band 9, p. 537. 

f Journ. d. Pliarm. et de Chim., 1869, p. 95. Zeitsclir. f. analyt. Chem., 
Band 8, p. 522. 

X ArcMv d. Pliarm.. Band 139, p. 19. 

§ Deutscli. Archiv f. klin. Med., Band 10, p. 319. 

II Virchow's Arcliiv, Band 60, p. 488. 



QUANTITATIVE ESTIMATIONS. 299 

well as the albuminous bodies mentioned by C. Gerliardt,^ 
wliich are not identical with albumen, and lastly, uric acid, 
mucus, and some other substances. Therefore, we cannot let 
the precii:)itation with alcohol pass as a method of estimating 
albumen. , 

6. L. Girgensohis 3Iethod.\ This method is founded on the 
fact that tannin completely precipitates albumen, and that all 
of the tannin can be withdrawn again from the compound of 
tannin and albumen by boiling with alcohol. In performing 
the test a definite quantity of urine is treated with half its vol- 
ume of a 20 per cent, solution of chloride of sodium, and then as 
much solution of tannin is added as is necessary for the com- 
plete precipitation of the albumen. The precipitate is collected 
in a weighed filter, washed with distilled water until the chlo- 
rine reaction disappears, and then with boiling alcohol as long 
as any tannin can be detected in the filtrate. The residue is 
dried and weighed. It might be well to remove the uric acid 
first by rendering it slightly acid with acetic acid, and allowing 
it to stand in the cold. 

This method, also, is not free from the criticism which must 
be made of the precipitation with alcohoL Tannin by no means 
precipitates the albumen alone from the urine, but at the same 
time a number of other bodies. 



§ 76. Calcium and Magnesium. 

I. ESTIMATION OF CALCIUM. 

A. Principle. The method of estimating calcium depends on 
the fact that all of the calcium is precipitated from an acetic 
acid solution of the phosphate of calcium in the form of an 
oxalate by oxalate of ammonium, and that oxalate of calcium is 
transformed by a red heat into carbonate of calcium and caustic 
lime, whose amount is determined by standard solutions of hy- 
drochloric acid and sodic hydrate. 

B. Preparation of the Solutions. 
1. Standard Hydrocliloric Acid. 

The hydrochloric acid which is used for this estimation of 

* Centralblt. f. d. med. Wissenscliaft. , 1869, p. 174. 
f Deutsch. Arcliiv f. klin. Med., Band 11, Heft 6. 



300 ajvalysis of the ubine. 

calcium is best so standardized that eacli cc. corresponds to ex- 
actly 10 mgrm. of calcic oxide. One liter of the acid, therefore^ 
must saturate 10 grm. of calcic oxide, or 18*93 grm. of carbo- 
nate of sodium. To prepare such an acid we twice weigh off an 
accurate quantity (about 1 or 1*2 grm.) of pure carbonate of 
sodium, previously ignited, and dissolve each portion separately 
in a flask in water, heat to boiling, after the solution is treated 
with a few drops of tincture of litmus, and then let the dilute 
hydrochloric acid flow into it until the blue color of the solu- 
tion has changed to onion red, which does not disappear again 
on further boiling. (The purpose of the boiling is to remove 
the carbonic acid which has been set free, so that the transi- 
tion of the wine-red color, which is caused by the carbonic acid, 
into the onion red shall come out sharply.) The experiment is 
repeated with the second quantity of carbonate of sodium, and 
from the results obtained the quantity of hydrochloric acid in 
the liter is reckoned by taking the average of the two. If, for 
example, we have found that one liter of the hydrochloric acid 
corresponds to 41 "4 grm. of carbonate of sodium, then 457 cc. 
will exactly saturate 18*93 grm. If we, therefore, measure off 
457 cc. from the hydrochloric acid thus tested, and dilute it to 
a liter, it has the required strength. 1 cc. then corresponds to 
0*0189 grm. of carbonate of sodium, or O'OIO grm. of CaO. A 
control ex23eriment with carbonate of sodium must confirm the 
accuracy of the dilution. 

2. Standard Sodic Hydrate. 

The sodic hydrate must exactly correspond to the hydro- 
chloric acid, 10 cc. of it must, therefore, exactly saturate 10 cc. 
of the hydrochloric acid, so that after the addition of the last 
drop of the 10 cc. of sodic hydrate, the red color of the hydro- 
chloric acid changes to a clear blue. "We must be especially 
careful that the sodic hydrate is completely free from carbonic 
acid, so that the transition of color may be sharply recog- 
nized. 10 cc. of the hydrochloric acid are now measured off 
with a pipette, it is allowed to flow into a small beaker, it is 
colored red with a few drops of tincture of litmus, and then 
the sodic hydrate is added until it is a clear blue. If 8 cc. of 
sodic hydrate have been required to 10 cc. of hydrochloric acid, 
we measure off 800 cc. and dilute it to a liter. Equal volumes 
of the two will then accurately saturate each other. The accu- 



QUANTITATIVE ESTIMATIONS. 301 

racy of the dilution is tested by a new experiment ; if after the 
last drop of the 10 cc. of sodic hydrate the red color of the 
10 cc. of hydrochloric acid has become a clear bine, the sodic 
hydrate is fit for use in the estimation. 

C. Performance. Exactly 100 or 200 cc. of the urine previ- 
ously filtered are measured off with a pipette, allowed to flow 
into a beaker, and ammonia is added until an abundant precipi- 
tate has taken place, which is then caused to disappear by the 
careful addition of acetic acid. The calcium is precipitated 
from the acetic acid solution thus obtained, which must con- 
tain only a few drops of acetic acid in excess, by oxalate of 
ammonium, and the glass is allowed to stand covered in a 
warm place until the precipitate has completely settled and 
the supernatant fluid has become perfectly clear. In most 
cases after six or eight hours the fluid can be drawn off clear 
by a siphon, which is always to be preferred to slow filtering 
when it can be performed witliout loss. The rest of the fluid 
with the calcic oxalate is poured on to a small filter free from 
calcium and thoroughly washed with water. (Filtrate and 
wash water are put aside for determining the magnesium.) 
The filter and the precipitate, still moist, are placed in a small 
platinum crucible, dried and ignited antil all of the carbon 
is consumed. The lime, which has become partly caustic, is 
carefully rinsed into a small flask, 10 cc. of the standard hy- 
drochloric acid are added and cautiously warmed until the 
whole is dissolved and the carbonic acid is expelled. Then 
after the solution has been colored faintly red by two or three 
drops of tincture of litmus, the non-saturated part of the hydro- 
chloric acid is titrated back with the sodic hydrate solution 
until the blue color appears. If the number of cc. of sodic hy- 
drate used up to this point are subtracted from the 10 cc. of 
hydrochloric acid added, we obtain the number of cc. satu- 
rated by the lime, each one of which corresponds to 10 mgrm. 
of calcic oxide. If then we multiply the number of cc. of hy- 
drochloric acid saturated by 10, we obtain directly the per- 
centage of lime in the urine, if 100 cc. were taken for the esti- 
mation. (See Analytical Experiments.) If we wish to calculate 
the lime found as phosphate, 1 cc. of the hydrochloric acid cor- 
responds to 18'45 mgrm. of SCaOPOg. 

Gravimetric Estimation, We proceed as above by precipi- 



302 ANALYSIS OF THE URINE, 

tating tlie calcium in tlie form of oxalate from 200 cc. of urine 
made acid with acetic acid. The washed and dried calcic oxa- 
late, freed from the filter, is then placed in a weighed platinum 
crucible and ignited for a considerable time after the filter has 
been completely reduced to ashes on the cover. After cooling 
the crucible, the calcium, which has become partially caustic 
during the ignition, is moistened with a few drops of pure 
dilute sulphuric acid, when a loss may easily occur, and, 
therefore, the crucible must be covered as closely as possible 
during the operation. After heating a second time the calcium 
remains behind as a sulphate ; the crucible is allowed to cool 
over sulphuric acid and is weighed. After subtracting the 
weight of the crucible and filter ash we obtain the amount of 
sulphate of calcium from which the corresponding amount of 
phosi3hate of calcium is reckoned. More easy still than evapo- 
rating and heating to a red heat with sulphuric acid is the 
conversion of the calcic oxalate' into sulphate by pure ammo- 
nium sulphate. (Schr otter.) 

Three equivalents of sulphate of calcium correspond to one 
equivalent of phosphate of calcium, having the composition 
3CaO,PO.. If, therefore, we multiply the amount of sulphate of 
calcium obtained by if J = 0-7598, Ave obtain the corresponding 
amount of phosphate of calcium. If, on the other hand, we 
wish to reckon the sulphate of calcium as CaO, we must multi- 
ply the amount found by 04118. 

II. ESTIMATION OF THE MAGNESIUM. 

1. B^J WeigUncj. The fluid filtered from the calcic oxalate is 
treated with ammonia until the reaction is alkaline, by which all 
of the magnesium is precipitated as ammonio-magnesian phos- 
phate. When the precipitate has completely settled after a 
few hours, it is collected on a filter, the weight of whose ash 
is known, washed thoroughly with water, to which \ of its 
volume of ammonia has been added, and dried. When this 
is accomplished, the precipitate is separated as completely as 
possible from the filter, it is put into a weighed platinum cru- 
cible, the filter is folded, and a thin platinum wire wound round 
it spirally, and it is ignited in the upper cone of the flame, 
which abounds in oxygen. This operation with phosphate of 
magnesium, otherwise so wearisome, is rendered very much 



QUANTITATIVE ESTIMATIONS, 303 

easier and shorter by this procedure ; the ash becomes pure 
and white after a very short time. When the ignition has 
been accomplished the filter ash is added to the precipitate, 
the cover is placed on the crucible and it is heated a long time, 
at first very gently, but at last at the strongest red heat, with 
the cover off; it is then allowed to cool over sulphuric acid 
and weighed. The ammonio-magnesian phosphate precipi- 
tated from the urine in this way is, however, always mixed 
with organic matters, especially uric acid, which on heating 
yield a carbon difficult to ignite, and which, therefore, renders 
a very long-continued ignition of the precipitate necessary and 
with the crucible uncovered. It is, therefore, best to place a 
small piece of nitrate of ammonium on the ammonio-magne- 
sian phosphate in the crucible after the filter has been ignited 
in the manner described, moisten it with a drop of water, 
dry, and heat first very gently, and lastly to a powerful red 
heat. The charcoal completely disappears, and we obtain the 
phosphate of magnesium very readily in this manner of daz- 
zling whiteness. The ammonio-magnesian phosphate becomes 
pyrophosphate of magnesium (2MgO,POi) on ignition; after 
subtracting the weight of the crucible and the filter ash an 
amount remains behind which, added to the quantity of pyro- 
phate of calcium calculated and found, gives the whole amount 
of earthy phosphates (phosphates of calcium and magnesium) 
in the urine taken. If, however, we wish to calculate the pure 
phosphate of magnesium found (SMgOjPOj) as pure oxide (MgO), 
we must multiply the amount obtained by ^fyy-? ^^^^ is = 0'3604, 
since 111 parts of pyrophosphate of magnesium correspond to 
40 of pure magnesic oxide. 

The earthy phosphates are determined more accurately and 
quickly in two amounts of urine, as follows : 

a. The amount of phosphate of calcium (3CaO,P05) in 200 
cc. of filtered urine is accurately determined according to the 
method given in § 76, i. C. Each cc. of hydrochloric acid satu- 
rated corresponds to 18*45 mgrm. of phosphate of calcium. 

b. Another 200 cc. of the filtered urine are precipitated 
with ammonia and allowed to stand six or twelve hours to 
completely separate and deposit all of the earthy phosphates. 
The fluid is then drawn off with a siphon, as far as this can be 
done without loss ; the precipitate is collected on a filter, the 



304 AliALYSIS OF THE URINE. ' 

weight of whose ash is known, it is washed with water con- 
taining ammonia (three parts of water and one part of ammo- 
nia), and the magnesium estimated exactly as was indicated 
in § 76, II. 1. This second estimation gives the whole amount 
qf earthy phosphates (2MgO,PO- + 3CaO,P05) contained in the 
urine. If we subtract the phosphate of calcium found in 1 
from it, the remainder is the amount of phosphate of magne- 
sium in the urine. 

2. Volumetricallij. The magnesium is precipitated from 200 
cc. of urine by ammonia, after the calcium has been removed 
by oxalate of ammonium ; the ammonio-magnesian phosphate 
is collected on a small filter after a few hours and washed with 
water containing ammonia. The filter is then broken through 
with a glass rod, the precipitate washed into a beaker and dis- 
solved with acetic acid. (If a little uric acid remains behind 
here, as has repeatedly happened in my analyses, the solution is 
best filtered from it.) The phosjohoric acid is then determined 
in the fluid obtained exactly according to § 67, C, b. The amount 
of phosphoric acid found multiplied by 0*563 gives the corre- 
sponding amount of pure magnesia (MgO) ; on the other hand, 
multiplied by 1-563 it gives the corresponding quantity of pyro- 
phosphate of magnesium. 

III. INDIRECT ESTIMATION OF CALCIC AND MAGNESIC PHOSPHATES. 

As is known there is no true separation attained by indirect 
analyses, but ulterior circumstances are brought about, from 
which we can calculate the acids and bases found together. If, 
for example, we have to determine potassium and sodium, the 
analysis can be made in such a manner that the two are changed 
into sulphates ; if these are weighed and the whole amount of 
sulphuric acid in them determined, the amounts of potassium 
and sodium can be calculated from these data. This is the 
case with the calcium and magnesium contained in the urine in 
combination with phosphoric acid. To perform this estima- 
tion we precipitate the earthy phosphates in two specimens of 
200 cc. of filtered urine by means of ammonia, filter it after a 
few hours, and determine one amount gravimetrically according 
to § 76, 11. 1. The second amount is washed into a beaker, 
dissolved in acetic acid, and the phosphoric acid in it titrated 



Q UAI^TITA TIYE ESTIMA TI0N8. 305 

exactly according to § 67, C, b. Tlie result is calculated for 
the twenty-four hours' amount of urine. 
We now know : 

a. The amount of the earthy phosphates 

(MgO)„,PO. f ^^ twenty-four hours. 

b. The amount of phosphoric acid for twenty-four hours cor- 
responding to the calcium and magnesium. 

An example will now explain the calculation in the simplest 
and clearest manner. 

Let us assume that the above estimations had shown that a 
daily amount of urine contained 1 grm. of earthy phosphates, 
and the phosphoric acid combined with the earths amounted to 
0*579 grm. The amounts of calcic and magnesic phosphates 
are reckoned as follows : 

If all ihQ PO5 were combined with calcium, the earthy phosphates 
should weigh 1*264 grm., according to the following proportion : 

71 : 155 = 0-579 : x. 

(PO5) [(CaO)3,P05] (amount of PO5 found.) 
x=l'2%^ grm. 

Since the total earthy phosphates, however, weigh less (grm. 1), 
phosphate of magnesium is also present in an amount proportional 
to the difference. 

1*264-1*000 3:^0*264. 

This quantity of magnesian-phosphate is obtained from the fol- 
lowing proportion : 

The difference between the equivalents of phosphate of calcium 
(155) and phosphate of magnesium (111), that is 44, is to the 
equivalent of phosphate of magnesium (111), as the difference found, 
0*264, is to the phosphate of magnesium present. 

44 : lll=:0-264 : x. 
ic=0*666 grm. (MgO)o,P05. 

We have then the total earthy phosphates =1*000 grm. 

The calculated amount of phosphate of magnesium =^0 -666 " 

Leaving (CaO)3,P05 =0.334 grm. 

20 



300 ANALYSIS OF THE URINE. 

From this consideration the following short, universally ap- 
plicable method of calculation may be deduced : 

The amount of phosphoric acid in the mixture is multiplied by 
2*1831, from the product the amount of the earthy phosphates is 
subtracted, the remainder is multiplied by 2*5227, and the product is 
the amount of the phosphate of magnesium contained in the mixture. 
If we designate the amount of the earthy phosphates found by S, 
and the PO5 obtained by P, the calculation may be simply expressed 
by the following formula : 

(P. 2-1831-S) 2*5227. 

If we wish to calculate the calcium and magnesium in the amounts 
of phosphate of calcium and of magnesium obtained, the following 
formulae are used : 

(CaO)3P05 X 0-5420 = CaO. 
(MgO),P05 X 0-3604 = MgO. 

§ 77. ESTBIATION OF AmMONIA. 

A. Principle. This method of estimating the quantity of am- 
monia, first mentioned by Schlusing, depends simply on the 
fact that an aqueous solution containing free ammonia suffers 
its ammonia to escape at ordinary temperatures in a relatively 
short time when exposed to the air, and that dilute sulphuric 
acid absorbs all of the ammonia contained in a closed space. 
If, therefore, we place an aqueous solution of ammonia together 
with a measured volume of standard sulphuric acid in a closed 
space, all of the ammonia in a short time will have combined 
with the sulphuric acid and have saturated an equivalent 
amount of it, which may be readily ascertained by titrating 
back the non-saturated portion with a standard sodic hydrate 
solution. 

B. Preparation of tlie Solutions. 
1. Standard Sulp)huric Acid. 

14 grm. of hydrate d sulphuric acid are diluted with 200 grm. 
of water, and when the mixture has become cool the strength 
of this dilute acid is determined in the usual way by precipi- 
tating two specimens of 10 cc. each with chloride of barium. 
If the two analyses agree we accept the result as correct. If, 
for example, we find that 10 cc. of the dilute acid contain 0*505 
grm. of sulphuric acid, then they will be exactly saturated by 



QUANTITATIVE ESTIMATIONS. 



307 



0*2146 grm. of ammonia (NH3) ; therefore, 1 cc. of the dilute 
acid corresponds to 0'02146 grm. of ammonia (NH,). 

2. Standard Sodic Hydrate Solution. 

We determine how large a volume of a good sodic hydrate so- 
lution, free from carbonic acid, is required to saturate 10 cc. of 
the standard sulphuric acid. For this purpose 10 cc. of the 
standard sulphuric acid are put in a small beaker, a few drops 
of tincture of litmus are added, and the sodic hydrate solution 
dropped from a pipette until the fluid just becomes blue. If 
we have used 30 cc. of the sodic hydrate solution up to this 
point, we know that each cc. of it corresponds to "00715 grm. 
of ammonia, because 10 cc. of the sulphuric acid (correspond- 
ing to 0*2146 grm. of NH^) have been exactly saturated by 30 
cc. of the sodic hydrate solution. 

C. Process. A flat glass or porcelain vessel (a beaker broken 
off an inch from the bottom is suitable for the purpose) is 
placed on a plate of ground glass which is smeared with tallow, 
and 10, or better, 20 cc. of the urine which is to be tested, 
freed from mucus by filtration, are introduced into it. A tri- 
angle made of glass rod is then laid on the vessel, and on the 
triangle a flat dish with low sides containing 10 cc. of the 
standard sulphuric acid is placed. A bell glass with a ground 
edge and smeared with tallow is then placed over the whole 
apparatus, so that an hermetically closed space is thus obtained. 
Fig. 37 shows the whole ap- 
paratus. When the appara- 
tus is all prepared, the bell 
glass is raised, a sufficient 
quantity of milk of lime (10 
cc.) is added to the urine from 
a pipette not drawn out at 
the end, and the bell glass is 
immediately firmly replaced. 
After forty-eight hours the 
whole of the ammonia has 
been expelled from the 10 or 
20 cc. of urine and absorbed 
by the sulphuric acid. If the 
non-saturated sulphuric acid is titrated back with the sodic 
hydrate solution, we ascertain the amount saturated by the am- 



Fm. 37. 




308 ANALYSIS OF TEE UEINE. 

monia, and consequently the quantity of ammonia in the 20 cc. 
of urine. 
Example : 

10 cc. of sulphuric acid = 0.505 grm. 803 = 0-2146 grm. NH3. 
They require 30 cc. of sodic hydrate solution ; 1 cc. of sodic hydrate 
solution, therefore, corresponds to ^-\\^^ = 0-00715 grm. of NH3. 

At the end of the experiment 26 cc. of the sodic hydrate 
solution have been required in titrating back. Therefore, an 
amount of NH3 has been evolved which corresponds to 4 cc. 
of the sodic hydrate solution. The 20 cc. of urine, therefore, 
contain 4 x 0-00715 = 0*0286 grm. NHa = 1-43 NH, per thousand. 
From my own experiments it appears that perfectly normal 
fresh urine does not undergo the alkaline fermentation in forty- 
eight hours ; but these experiments must not be taken as the 
rule in all cases, since many urines, as we well know, very soon 
become alkaline. I consider it safer, therefore, to make a con- 
trol experiment, in addition to the regular estimation of ammo- 
nia, by placing a like amount of the same urine in a second 
apparatus without milk of lime and observing the result. If 
we find that the urine readily becomes decomposed, it is better 
to first remove the coloring and extractive matters. We pre- 
pare for this purpose a mixture of acetate and basic acetate of 
lead solutions, an equal volume of each, measure off 30 cc. of 
the urine, add to it an equal quantity of the lead solution, filter, 
and take 40 cc. from the clear filtrate corresponding to 20 cc. of 
urine for the estimation of the ammonia. This precaution is 
quite unnecessary with a normal fresh urine, as my experi- 
ments show.^ This method gives very satisfactory results. 
(Analytical Experiments.) 



§ 78. Estimation of the Ammonia and Potash by means of 
Platinic Chloride. 

A measured quantity of urine, 20 or 30 cc, are placed in a 
beaker, and a sufficient quantity of platinic chloride and three 
times its volume of a mixture of alcohol and ether are added. 
After twenty-four or thirty-six hours, when no further precipi- 

* Joum. f. pract. Chemie, Band 64, p. 177. 



QUANTITATIVE ESTIMATIONS. 309 

tation is seen to take place, it is filtered, well washed with 
alcohol to which a little ether has been added, and dried. 
The precipitate, together with the filter, is then placed in a 
platinum crucible and ignited, the crucible being covered at 
first, until the carbon of the filter is wholly consumed, which 
process may be very much hastened by giving the crucible an 
oblique position. The remaining mass is then treated with hot 
dilute hydrochloric acid as long as the acid takes up anything ; 
the platinum which remains behind is placed on a filter, the 
weight of whose ash is known, carefully washed with hot 
water, and the filtrate obtained preserved for estimating the 
potassium by the method to be mentioned directly. After ig- 
niting and weighing, by subtracting the weight of the filter 
ash and crucible, we obtain the quantity of platinum which cor- 
responds to the amount of ammonia and potassium contained 
together in the urine. 

In order now to determine the quantity of the potassium, the 
hydrochloric acid solution, together with the wash water which 
contains the whole of the potassium, is reduced to a small 
volume (1 or 2 cc.) by evaporation, it is precipitated by thirty 
drops of platinic chloride solution and a mixture of alcohol 
and ether as mentioned above. After twenty-four hours the 
precipitate which is obtained, and which contains all of the 
potassium as potassio-platinic chloride, is placed on a filter, 
washed with alcohol and ether, dried, ignited with the filter as 
above, extracted with hydrochloric acid, the remaining plati- 
num collected on a filter, the weight of whose ash is known, 
dried, ignited, and weighed. After subtracting the weight of 
the filter ash, we obtain the quantity of platinum which corre- 
sponds to the potassium. The difference between this amount 
of platinum and that obtained at first corresponds to the quan- 
tity of ammonium. If, for example, we find the whole amount 
of platinum to be 0*1980 grm. for the potassium and ammonium 
contained in 30 cc. of urine, and for the potassium alone by the 
second estimation 0"1330, there remains for ammonia 0'065 
grm. of platinum (0-1980 -0-1330). 

One hundred parts of platinum correspond to 17-182 parts of 
ammonia, therefore 0-065 platinum (100 : 17*182 = 0-065: a;) x = 
0*01116 ammonia in 30 cc. of urine. 

We calculate in the same way the amount of potassium pres- 



310 ANALYSIS OF THE URINE. 

ent from the amount of platinum employed in separating it; 
100 parts of platinum correspond to 47*61 parts of potassic oxide. 

§ 79. Estimation of the Potassium and Sodium. 

A. Direct Determination. 30 cc. of urine are mixed with 30 
cc. of baryta solution (two volumes of baryta water and one 
volume of a cold saturated solution of nitrate of barium, see 
§ 65, B, 3), it is allowed to stand for a time, filtered, 40 cc. of 
the filtrate are measured off, corresponding to 20 cc. of urine, 
and evaporated to dryness in a platinum capsule on the water 
bath. The residue is then heated over a free flame, at first very 
gently to avoid decrepitation and too sudden combustion, af- 
terward strongly, and the heat is continued until the greater 
part of the carbon has been consumed. Yet we must guard 
against too strong a heat lest a part of the chlorides should 
volatilize. The residual mass is then extracted with hot water, 
acidulated with hydrochloric acid, and treated, without previous 
filtration, with a solution of ammonia and carbonate of ammo- 
nium as long as a precipitate is thrown down, it is filtered, the 
precipitate thoroughly washed, and the filtrate, after acidulating 
with hydrochloric acid, is evaporated again to dryness in the 
platinum capsule. After the residue has become perfectly dry 
it is carefully heated to drive off the ammonium salts, but in 
such a manner as not to suffer any loss from decrepitation, the 
residue is again dissolved in a little water, a few drops of ammo- 
nia and carbonate of ammonium are again added, the mixture 
filtered, the precipitate carefully washed and the filtrate again 
evaporated to dryness, but this time in a previously weighed 
platinum capsule. The thoroughly dry residue is gently heated 
to drive off the ammonium salts, it is then left to cool in the 
desiccator and weighed. We thus obtain the whole quantity of 
potassium and sodium in the form of chlorides. To separate 
the two the weighed amount of alkaline chlorides is dissolved 
in a little water, chloride of platinum added in considerable 
excess, and the mixture evaporated almost to dryness on the 
water bath. The residue is then treated with alcohol of 80 per 
cent, and allowed to stand several hours with frequent stirring. 
When the sodio-platinic chloride is dissolved, and the superna- 
tant fluid has a deep yellow color, a sign that sufficient chloride 
of platinum has been added, the potassio-platinic chloride is 






QUANTITATIVE ESTIMATIONS. 311 

collected on a filter wliicli has previously been dried at 100° C. 
and weighed, washed with alcohol, dried at 100° C and weighed. 

From the potassic-platinic chloride obtained the correspond- 
ing amount of chloride of potassium is calculated (100 parts of 
potassio-platinic chloride correspond to 30*51 parts of chloride 
of potassium), and this subtracted from the whole quantity of 
the alkaline chlorides gives as the difference the amount of 
chloride of sodium. 

The amount of chloride of potassium obtained gives when 
multiplied by 0*6317 the corresponding amount of potassic ox- 
ide ; the chloride of sodium multiplied by 0*5302 gives the cor- 
responding amount of sodic oxide. 

B. Indirect Determination. The potassium and sodium can be 
calculated indirectly, though this method is inferior to the 
former in accuracy. The principle of the indirect analysis has 
already been given in § 76, in. After the whole quantity of 
chloride of potassium and chloride of sodium has been accu- 
rately determined by weighing, according to A, the saline mass 
is dissolved in water, the solution is introduced into a beaker, 
the vessel thoroughly washed with water, and, after the addition 
of a few drops of a solution of neutral chromate of potassium, 
the whole amount of the chlorine is determined by means of a 
standard solution of nitrate of silver according to § QQt. If we 
know the total amount of the chlorides of potassium and sodium, 
as well as the total amount of chlorine, the quantity of potassium 
and sodium can be reckoned from these data. 

The amount of chlorine in the mixture is multiplied by 
2*1029, the amount of the metallic chlorides is subtracted from 
the product, and the remainder is multiplied by 3*6288. We 
thus find the quantity of chloride of sodium contained in the 
saline mass, and this, subtracted from the total metallic chlo- 
rides, gives the quantity of chloride of potassium. 

Chloride of potassium x 0*6317 = potash (KO). Chloride of 
sodium X 0*5302 = soda (NaO). 

Experiments to determine the quantity of potassium by pre- 
cipitating the previously concentrated urine with tartaric acid 
did not give favorable results. On account of the impurity of 
the acid tartrate of potassium obtained the results were con- 
stantly too high. (Salkowski.)* 

* Pfliiger's Archiv, Band 6, p. 209. 



312 AJSTALYSIS OF THE URINE. 

§ 80. Estimation of the Carbonic Acid. 

According to Marchand,^ the free carbonic acid in the urine 
can be estimated in the following way : About 100 cc. of the 
urine to be tested are placed in a glass flask which is fitted 
with an air-tight, doubly perforated stopper. A tube which 
dips into the urine and is drawn out to a fine, easily fusible 
point at the other end, is passed through one opening of the 
stopper ; while through the second opening a doubly bent tube 
is passed, one of wdiose arms enters an empty flask through an 
air-tight stopper. This flask is connected by a second tube with 
a similarly arranged flask filled with clear baryta water, which 
again is connected with one or two flasks half-filled with baryta 
water. The last of these is connected with an air pump. When 
the apparatus is prepared, the urine is heated on the water 
bath to 50^ or 60^ C. and the air slowly exhausted. The fluid 
soon commences to boil and to distil over into the empty flask, 
and the baryta solutions become cloudy from the separation of 
carbonate of barium. After half or three-quarters of an hour 
the fine point of the first tube is broken off and air is drawn 
through the apparatus. The precipitated carbonate of barium 
is carefully filtered off, and, after washing, dissolved in hydro- 
chloric acid, precipitated again by sulphuric acid, and weighed 
as sulphate of barium. From the quantity thus obtained we cal- 
culate the carbonic acid which w^as present. 116*5 parts by 
weight of sulphate of barium correspond to 22 parts by weight 
of carbonic acid. 



§ 81. Estimation of the Total Nitrogen in the Urine. 

As is well known the urine contains nitrogen in very different 
forms, such as urea, uric acid, kreatinin, ammoniacal salts, etc. 
It may be of importance in answering physiological questions to 
determine quantitatively the entire amount of nitrogen elimi- 
nated Avitli the urine in these different forms ; therefore I give 
here the method given by Voit and Seegen for this purpose. 

Since in estimating urea in the urine by Liebig's method, not 
only the urea is precipitated, but other nitrogenous constitu- 

* Journ. f iir pract. Chemie, Band 44, p. 253 



QUANTITATIVE ESTIMATIONS. 313 

ents of the urine also, such as kreatinin, etc., form compounds 
with the mercuric nitrate, we can, according to the investiga- 
tions of Yoit,"^ Parke s, and Wollowicz,t calculate from the urea 
found by Liebig's method, the total quantity of nitrogen with 
tolerable accuracy. Yoit found in an average of seventeen 
combustion analyses in 700 cc. of human urine 9*31 grm. of 
nitrogen, while 94 grm. were reckoned from the urea found. 
Parkes and Wollowicz found in twenty-six combustion analyses 
that the amount of nitrogen eliminated in twenty-four hours 
averaged 16*46 grm., while from the urea found by Liebig's 
method after precipitating the chlorine, 16*34 grm. of nitrogen 
were obtained on the average. S. Schenk:j: obtained results 
which differed somewhat ; he determined the nitrogen in hu- 
man urine by combustion with soda-lime and by Dumas's 
method, and in addition calculated from the urea obtained. 
While the two methods of estimating the nitrogen gave nearly 
the same results, the calculations from the urea showed devia- 
tions. In an average of eight estimations, combustion gave 
0*1395 grm. of nitrogen for 10 cc. of urine, while 0*1385 grm. 
was reckoned from the urea. The greatest deviations which 
Liebig's method gave in comparison with the direct determina- 
tion of nitrogen amounted to —0*014 and +0*021 for 10 cc. of 
urine ; if the twenty-four hours' quantity of urine had amounted 
to 1,000 cc, there would have been found 1*4 grm. of nitrogen 
too little or 2*1 grm. too much. Schenk on the strength of his 
experiments declares Liebig's method unserviceable, as well for 
estimations of urea as of nitrogen, and, consequently, for all ex- 
periments upon the metamorphosis of tissue ; and since the 
estimation of urea by the method of Heintz always gave less 
nitrogen than by other methods, he regards it as the most suit- 
able for ascertaining the true quantity of urea in the urine. 
Moreover, it has been shown that the deviations of the direct 
estimations of nitrogen and the quantities calculated from the 
urea by Liebig's method nearly balance in long series of experi- 
ments, and such only come in question in experiments upon 
the metamorphosis of tissue, by the averages reported by Yoit, 

* Zeitschrift f . Biologie, Band 2, p. 469. 
f Chem. Centralblatt, 1870, p. 631. 

X Centralblatt f. d. med. Wissenschaften, 1869, p. 853. Wiener Sitzungsbe- 
ricbt. 59, p. 162. 



314 AI^ALTSIS OF THE URINE. 

Parkes, and WoUowicz, as well as by those obtained by Schenk 
also. In conclusion, with regard to the estimation of urea by 
the method of Heintz and Ragsky, concerning which Schenk 
asserts that there is no suspicion that the results could prove 
too small, and that we know of no other body in the urine 
than urea which on heating with sulphuric acid yields am- 
monia, Heintz^" himself has shown that his method yielded 
for 1,000 parts of urine about 0'3 urea too much, since kreatin, 
oxaluric acid, and the extractive matters also gave a little am- 
monia on heating with sulphuric acid. Liebig's method will 
not deviate much more from the truth, and, therefore, will 
probably only be abandoned when a method is found which 
with the same ease will yield really absolute figures for the 
urea. 

A. Principle. All organic nitrogenous bodies which do not 
contain the nitrogen in the form of nitric acid, etc., are so de- 
composed by ignition with soda-lime that all of the nitrogen 
escapes in the form of ammonia, which can be easily collected 
in sulphuric acid of known strength, and be determined by 
titration. One equivalent of NHg^l?, corresponding to one 
equivalent of ^=14. 

B. Preparation of the Solutions. It is well to use for this pur- 
pose a dilute suljDhuric acid, which contains in 1,000 cc. exactly 
40 grm. of anhydrous sulphuric acid, and is therefore normal. 
60 grm. of concentrated English sulphuric acid are, therefore, 
v/eighed off, diluted with 1,020 cc. of water, and the amount of 
sulphuric acid in each 20 cc. of this dilute acid is then deter- 
mined by precipitation with chloride of barium. If, for instance, 
we have found that 20 cc. contain 0*840 grm. of sulphuric acid, 
then 1,000 cc. contain 42 grm. Therefore 1,000 cc. of this acid 
(40 : 1,000=42 : x) must be brought to 1,050 cc. by adding 50 cc. 
of water, in order to obtain an acid which is normal, that is, con- 
tains exactly 1 equivalent of 863=40 grm. in the liter. Each cc. 
of this acid corresponds to jo'oo equivalent of nitrogen =0*014 
grm. 

Standard Sodic Hydrate Solution. This must be equivalent to 
the sulphuric acid, that is, equal volumes of the two must ex- 
actly saturate each other. 20 cc. of the dilute acid, colored 

* Heintz, Lehrbuch der Zoochemie, p. 179. 



QUANTITATIVE ESTIMATIONS. 315 

feebly red with tincture of litmus, must be exactly neutralized 
by 20 cc. of the sodic hydrate solution, free from carbonic acid, 
so that after the addition of the last drop of the 20 cc. of the 
sodic hydrate solution, the red color of the sulphuric acid 
changes to a clear blue. (To prepare such a sodic hydrate so- 
lution, see § 76, B, 2.) 

C. The Distilling Apparatus. This consists of a strong flask 
of about 100 cc. capacity, whose neck, which is 10 or 12 ctm. 
long, is closed by a doubly perforated rubber stopper. One hole 
in the stopper receives a bent glass tube, e, which is connected 
with a Varrentrapp-Will nitrogen apparatus, /. A straight 
glass tube with an opening two mm. in diameter is passed 
through the other hole and serves to aspirate air through the 
apparatus after the completion of the combustion, so that the 
products of combustion may be carried over into the receiver; it 
therefore extends into the body of the flask nearly to the soda- 
lime. The outer end of this tube is drawn out to a point and 
hermetically sealed. After the end of the combustion the point 
is broken off. The flask is placed in a sand bath of copper plate, 
and to prevent the deposition of water on that portion of the 
neck of the flask uncovered by sand, the latter is surrounded 
by a metallic cover, c, which reaches to the stopper. The sand 
bath is heated by a Bunsen lamp. A good flask suffices for 
many estimations. The whole arrangement of the apparatus is 
shown in fig. 38, on the following page. 

D. Process. 20 cc. of the standard sulphuric acid are intro- 
duced into the nitrogen apparatus first, soda-lime freshly ignited 
is put into the flask, so that the bottom is covered about 1*5 
ctm. deep, and then the whole apparatus is put together. When 
this is accomplished 5 cc. of urine are allowed to flow on to the 
soda-lime, and the stopper is quickly introduced. The soda- 
lime must be sufficient in quantity to absorb all of the urine, 
and it must be uniformly saturated by the urine, so that no 
layer of fluid remains standing above it. The sand bath is filled 
with sand up to its edge, so that the metallic cover stands in 
the sand, and then it is heated as long as any evolution of 
gas is observable. Heating for half an hour to a red heat is suf- 
ficient to expel into the receiver all of the nitrogen in the form 
of ammonia from 5 cc. of urine. When the liberation of gas 
has at last wholly ceased, the fine point of the tube d is broken 



316 



ANALYSIS OF THE URmE. 



off and air is drawn through the apparatus by means of a rub- 
ber tube drawn over the end of the receiver, so that the last 
traces of ammonia are brought into the sulphuric acid. The 
combustion is now finished, the nitrogen apparatus is removed, 
the sulphuric acid is poured into a beaker, thoroughly rinsed 



Fig 




out with water, and the non-saturated sulphuric acid titrated 
back with the equivalent sodic hydrate solution. Each cc. of 
the sulphuric acid saturated by the ammonia set free indicates 
0*014: grm. of nitrogen. 
Example : 

One cc. =0*014 grm. of nitrogen. The quantity of urine passed 
in twenty-four hours ==1200 cc. 5 cc. of urine were used in the 
analysis. Of the 20 cc. of sulphuric acid contained in the nitrogen 
apparatus 7*5 cc, as determined by titrating back with the sodic 
hydrate solution, were saturated, which, therefore, corresponded to 
7*0 X 0*014 grm. =: 0*1050 grm. nitrogen. 

The total quantity of nitrogen eliminated with the urine in twenty- 
four hours : 

5 : 0*1050 = 1200 : a; = 25*2 grm. 



QUANTITATIVE ESTIMATIONS. 317 

If a large air pump is available, the following procedure may 
be adopted, according to Voit : * Fine ignited quartz sand is 
placed in a very shallow porcelain capsule of about 8 cm. dia- 
meter, a glass cover is then fitted on its broad edge, and the 
whole apparatus is weighed. 5 cc. of urine are then allowed to 
flow from a small accurate pipette on to the quartz powder, 
which must be present in sufficient quantity to completely 
absorb the fluid, and the apparatus is weighed once more to 
confirm the measurement. The uncovered dish is now placed 
under the bell of the air pump together with sulphuric acid, and 
in a few hours the caked mass becomes so dry that it can be re- 
moved in fine powder by scraping from the walls of the dish 
with the back of a broad knife. The powder thus obtained is 
mixed with soda-lime and ignited as usual in a combustion tube. 
The liberated ammonia is collected in standard sulphuric acid, 
which is best kept in a U-shaped tube, and the quantity deter- 
mined as given above by titrating back the non-saturated acid. 

The estimation of nitrogen is best combined with that of the 
total solids of the urine according to my method (§ 59, 2). The 
process is completed as usual, except that in collecting the 
ammonia a U-shaped tube is used instead of a small flask, and 
quartz sand instead of bits of glass. The ammonia set free by 
evaporating the urine and drying the residue is titrated in the 
usual way, calculated as urea, and the urinary residues found 
by weighing are added to it. If all of the solid constituents of 
the urine have thus been determined, the combustion in the 
tube with soda-lime is performed with the dry residue, but the 
amount of ammonia already determined, which was formed by 
the evaporation, etc., from the decomposition of the urea, is 
added to that last obtained. 

The small quantity of nitrites or nitrates which every urine 
contains does not" derange the result, since according to investi- 
gations of E. Schulze t small quantities of nitric acid, in the 
presence of large quantities of organic matter, are likewise com- 
pletely changed into ammonia on being ignited with soda-lime. 

* Zeitschrift f. analyt. Chem., Band 7, p. 398. 
f Zeitsclirift f. analyt. Chem., Band 6, p. 379. 



318 ANALYSIS OF THE UBINE, 

§ 82. Estimation of the Fat. 

Probably in the very rarest cases would it be of interest to 
determine quantitatively the fat which occurs in the urine, 
at most only in very small quantity. If such an estimation, 
however, is to be undertaken, 20 or 30 cc. of urine are evapo- 
rated to dryness on the water bath, and the residue obtained 
is dried in the air bath for a long time at 110°. In order to 
extract the fat, ether is poured over the residue, thoroughly but 
carefully mixed with it, and allowed to digest for some time 
with frequent stirring. The clear ether is then poured off into 
a light glass tube which has been weighed, fresh ether is added 
to the residue, and this operation is repeated until the ether 
takes up nothing more. The ethereal extracts are evaporated 
in the weighed glass cylinder and the residue which remains 
is calculated as fat. It must be observed, however, that in this 
calculation, when the urine contains free lactic acid, the weight 
of the ethereal residue will be thereby increased, since free 
lactic acid is also soluble in ether. It is well, therefore, to 
wash the residue repeatedly with water until it ceases to take 
up anything, and then to dry and weigh. 

§ 83. Estimation of the Biliaey Acids. 

Although even when icterus is very intense, only very small 
quantities of the biliary acids ever pass into the urine, still, ac- 
cording to Hoppe-Seyler,* they may be approximately estimated 
with the polarizing apparatus. The biliary acids are separated 
from at least 400 or 600 cc. of icteric urine according to the 
method given by Hoppe-Seyler and described in § 29. The 
alcoholic solution of the biliary salts, decolorized with animal 
charcoal if necessary, is next concentrated to a small volume, 
measured, and then examined with the polarizer according to 
§ 70, 3. Since now the specific rotation of cholate of sodium in 
alcoholic solution amounts to +314°, while that of sugar for 
medium white light amounts to +^&, the degrees read off on the 
scale and nonius must be recalculated. The per cent, of cholic 
acid in the alcoholic solution is found according to the formula 

* Dessen Handbuch, 3te Aufl., p. 286. 



QUANTITATIVE ESTIMATIONS. 319 

^•j,l ~2^i ^^^ the weight of the cholic acid in the amount of urine 
subjected to examination is found by the formula y^ • 31^4 = oc. 
In this formula a is the rotation found with an observing tube 
0*1 m. long, V the volume of the alcoholic solution of the cholate 
of sodium in cubic centimeters, and x the weight of the cholic 
acid contained therein. Moreover, if v, the volume of the alco- 
holic solution of cholate of sodium, corresponds to 500 cc. of 
icteric urine, | gives the percentage of the biliary salts in the 
urine. It is not always the case, as is here assumed, that only 
cholic acid is contained in the urine, but since the difference in 
the rotation of glycocholic and cholic acids is only very slight, 
the error caused thereby falls within the limits of errors of ob- 
servation, and may, therefore, be disregarded. (Hoppe-Seyler.) 

§ 84. Estimation of the Indican by Jaffe's Method.* 

Principle. If a colorless or feebly-yellow solution of indican 
is treated with about an equal volume of pure hydrochloric acid, 
then a few drops of a saturated solution of calcic hypochlo- 
rite are carefully added, and the mixture shaken, it instantly 
becomes of an intense blue color, and is rendered cloudy by 
the separated indigo, which in a few minutes becomes flocculent, 
and settles completely in a few hours. Human urine is very 
rarely blue or green, but usually assumes a red or violet shade 
after the addition of calcic hypochlorite ; nevertheless such a 
specimen after filtration leaves a distinct blue tinge on the 
filter. 

Process. 1,000 or 1,500 cc. of urine are rendered alkaline by 
milk of lime and the phosphates are completely precipitated 
by chloride of calcium. After standing twelve hours the mix- 
ture is filtered and the filtrate and wash water evaporated to a 
thick syrup, first over a free flame and then on the water bath. 
At the same time the reaction must be tested from time to 
time and finally a little carbonate of sodium added. The syrupy 
residue is warmed several minutes with about 500 cc. of strong 
alcohol, it is introduced into a beaker, left at rest for twelve or 
twenty-four hours for the complete separation of everything 

* Arcliiv f. d. g. Ptysiologie, Band 3, p. 448. Zeitschr. f. analyt. Cliem., 
Band 10, p. 126. 



320 ANALYSTS OF THE URINE. 

precipitable, it is then filtered and the alcohol distilled off. 
The residue is dissolved in a large quantity of water and pre- 
cipitated with a very dilute solution of ferric chloride, at the 
same time avoiding a great excess. The filtrate from the iron 
precipitate is treated with ammonia, heated to boiling, and 
after removing the ferric hydrate which has separated, it is 
evaporated to a volume of from 200 to 250 cc. With this fluid, 
which, as a rule, must be filtered once more, the estimation of 
the indigo is carried out as follows : First, the amount of cal- 
cic hypochlorite solution necessary to separate the indigo must 
be ascertained. For this purpose 20 or 40 cc. of the fluid are 
measured off and gradually diluted with measured quantities 
of water, until 10 cc. of the mixture treated with an equal vol- 
ume of hydrochloric acid assume a just perceptible blue color 
when one drop of a saturated solution of calcic hypochlorite is 
added ; the boundary of the reaction has then been reached. 
It has been found by many experiments that the number of 
volumes of dilution, which can be added to a solution of indi- 
can before the above limit occurs, amounts to about double the 
number of drops of the calcic hypochlorite solution which are 
necessary to produce the maximum sej)aration of indigo in 10 
cc. of the indican solution. If, then, the above experiment gave 
the last visible blue color after diluting with water eight times, 
for every 10 cc. of the undiluted urinary fluid, about four drops 
of the calcic hypochlorite solution are necessary for the com- 
plete decomposition of the indican, after diluting ten times five 
drops, etc., etc. 

We can, therefore, readily determine the necessary quantity 
of chlorine if we ascertain with a part of the urinary fluid at 
what dilution the indican reaction just disappears, and in order 
to be sure, for every 10 cc. we take one or two drops of calcic 
hypochlorite solution more than half the volumes of dilution. 
If we have thus found that the limit of the reaction has been 
reached at a dilution of eight times, we measure off 200 cc. of 
the urinary fluid, which correspond to a definite volume of the 
original urine, add an equal volume of hydrochloric acid and 
then the calculated number of drops of calcic hypochlorite 
solution drop by drop with constant stirring, in our case, there- 
fore, about 100 drops. We let it stand at least twelve hours 
to allow the indigo which has separated to deposit completely. 



QUANTITATIVE ESTIMATIONS. 321 

We then filter tlirough a very thick Swedish filter, previously 
extracted with hydrochloric acid, dried at 150^ C. and weighed, 
and wash successively with cold water, then with hot water, 
with dilute ammonia, and lastly once more with water, dry at 
105° or 110° C, and weigh. 

Jaffa found 4*5 to 19*5 mgrm. of indigo in 1,500 cc. of normal 
urine. Horse's urine contains on the average about twenty-five 
times as much indigo as human urine. J. Kosenstern ^ found 
a considerable increase of indican in the urine in Addison's 
disease. The amount of indican in this case amounted to 
from 53 to 80 mgrm. in 1,000 cc. of urine ; it averaged Q>4,'^ 
mgrm. 

§ 85. Estimation of the Oxalic Acid. 

For estimating quantitatively the oxalic acid which is pre- 
sent not as a sediment, we may follow the same method which 
I have given above, § 45, C, for detecting oxalic acid in urine 
which has not deposited a sediment. After standing twenty- 
four hours, the separated calcic oxalate is transferred to a 
small filter, the weight of whose ash is known, it is washed, 
dried, and the calcic oxalate transformed by a strong red heat 
into caustic lime. The amount of caustic lime obtained multi- 
plied by 1*6071 gives the corresponding amount of oxalic acid 
=G,HA [C,HA]. 

The method given by O. Schultzen t for the same purpose 
gives less reliable results, since, as Salkowski :j: states. Senator 
has proved that calcic sulphate is precipitated at the same 
time by this procedure. 

* Virchow's Archiv, Band 56, p. 27. 
f Reichert n. Dubois-Reymond's Arcliiv, 1869, p. 718. 
:j: Archiv fiir patholog. Anatom., etc.. Band 50. 
21 



DIVISION THIED. 

SYSTEMATIC COURSE OF QUALITATIVE AND QUANTITATIVE 
ANALYSIS OF URINE. 

I. Qualitative Analysis. 

§86. 

The qualitative analysis of a urine may naturally be per- 
formed in two different ways, according as we wish, to ascertain 
tlie presence or absence of any normal or abnormal constituent 
of the urine, or to obtain a complete qualitative representa- 
tion of the urine passed at any given time. In the first case a 
few tests are sufficient, as a rule, to obtain our object ; but in the 
second it is w^ell to follow a plan which includes all of the indi- 
vidual substances. The following section may be regarded as 
such a plan, in which consideration is taken of all of the nor- 
mal constituents of the urine, as well as of the most important 
and most common abnormal constituents ; while with regard to 
those which are more rarely met with, and those which require 
very large quantities of urine for their investigation, I must re- 
fer to the sections in Division First, in which they are treated. 
Moreover, since I have already described at length in Division 
First the processes for detecting all of the constituents of the 
urine, it will suffice here to give merely a schedule of the pro- 
cesses to be carried out, and with regard to their special per- 
formance to refer to the former sections. 

A. Systematic Peocess for Detecting the Soluble 
Constituents. 

§87. 

1. The reaction is tested with litmus paper, 
a. If the urine is acid and contains no sediment, we proceed 
as described in 2. 

322 



QUALITATIVE ANALYSIS. 323 

b. If the urine is acid and contains a sediment, we allow it 
to settle, pour off the clear urine, filter if necessary, and test it 
according to 2. 

The sediment is to be examined microscopically according to 
§ 88. 

c. The urine is neutral or alkaline. In this case there is 
usually a sediment in it ; the sediment is tested according to 
§ 88, and the filtered urine according to 2. 

2. A small portion of the urine rendered acid, if it is not 
already so, by a drop of acetic acid, is heated to boiling. If a 
coagulum is formed which does not disappear after the addi- 
tion of nitric acid, it consists of albumen. We then separate 
all of the albumen from a larger quantity of urine (500 or 600 
cc.) by boiling (§ 23, E), filter, and treat the filtrate according 
to 3. 

The reaction with nitric acid serves as a confirmatory test 
(§ 23, C, 9), also the test with carbolic acid by the method of 
Mehu, page 97. 

If the quantity of albumen is very small, the nitric acid is 
very carefully covered with a layer of the urine to be tested ; 
mere traces of albumen produce a turbidity in the form of a 
sharply defined zone at the point of junction of the two fluids 
(§ 23, E), at the end. 

The resulting coagulum is either : 

a. White, when it consists of pure albumen ; 

b. Greenish, when we have reason to suspect biliary matters, 
especially if the urine itself was deeply tinged (§ 28) ; 

c. Brownish red, when we may suspect the presence of blood ; 
we therefore test the sediment carefully, according to § 88, and 
test the original urine with the spectroscope according to § 51, 
B, 1 and 2. The dried coagulum is treated with alcohol and a 
few drops of sulphuric acid. If the fluid after filtration is 
more or less red, it is first tested for hsematin with the spec- 
troscope (§ 51, B, 2), then evaporated to dryness and ignited. 
The residue is heated with water to which a little hydrochloric 
acid has been added, it is filtered and the solution tested with 
sulphocyanide of potassium. The occurrence of a red color 
indicates the presence of iron. 

Hgematin in solution is tested by Heller's test (§ 51, B, 2, c). 
A specimen of the urine is heated to boiling, concentrated po- 



324 ANALYSIS OF THE UHINE. 

tassic hydrate is added and the color of the fluid observed, as 
well as the color of the earthy phosphates which are separated 
in flocculi after standing for a short time. 

Another specimen is treated with ammonia, then with tannin 
solution, and lastly with acetic acid until the reaction is dis- 
tinctly acid. The precipitate which may occur is treated 
exactly according to § 51, B, 2, d, and finally used for the pro- 
duction of hsemin crystals which are so characteristic of blood 
pigment. 

3. About 600 or 800 cc. of clear urine or of urine separated 
from its sediment or albumen coagulum by filtration are evapo- 
rated on the water bath to the consistence of a thick syrup, 
and the residue obtained is divided into two portions (J 
andf). 

a. One-third of this residue is extracted wdth strong alcohol, 
the undissolved portion is allowed to settle, the solution is 
filtered, the residue again washed once or twice with strong 
alcohol, and the solution tested as follows (aa), and the residue 
according to c. 

aa. A small quantity of the alcoholic solution is evaporated 
nearly to dryness on the water bath, and the residue tested for 
urea by adding nitric or oxalic acids (§ 2, D, 9, a and b). 

bb. The greater part of the alcoholic solution is treated 
with a few drops of milk of lime, and then with a solution of 
chloride of calcium as long as any precipitate is produced by 
it. The filtrate is evaporated on the water bath to 10 or 12 
cc, introduced into a beaker, and after cooling treated with J 
cc. of an alcoholic solution of chloride of zinc. After being- 
well shaken the mixture soon becomes cloudy and kreatinin- 
chloride of zinc is formed. The precipitate collected after a few 
hours is tested microscopically according to § 3, C, 1. 

Large quantities of kreatinin may be easily obtained as de- 
scribed in § 3, D, and § 5, D, 2. 

b. Two-thirds of the residue are slightly acidulated with hy- 
drochloric acid, rubbed up with powdered sulphate of barium, 
and then extracted with alcohol. The alcoholic solution is 
used for testing for Mjjpuric acid, as described in § 8, E. 

The crystals obtained are examined microscopically (Plate I, 
fig. 1), and, as far as the material serves, chemically also 
(§ 8, D, 7). 



QUALITATIVE ANALYSIS. 325 

The detection of hippnric acid according to § 8, E, 2, is very 
easy and certain. The kreatinin can be precipitated by chlo- 
ride of zinc solution from the urinary extract after exhaustion 
with ether, after it has been exactly neutralized with sodic hy- 
drate solution and diluted with 30 cc. of absolute alcohol. The 
saline mass precipitated from the eyaporated urine by absolute 
alcohol is tested for any succinic acid which may be present, 
as described in § 8, E, 2. 

c. The residue which has been obtained by treating with al- 
cohol, according to a, is covered with dilute hydrochloric acid 
(one part of hydrochloric acid and six parts of water) in the 
evaporating dish, and the undissolved portion separated by a 
small filter. 

aa. The hydrochloric acid solution contains the earthy phos- 
phates and other salts ; the former are precipitated by neutral- 
izing the solution with ammonia. 

bb. The residue which is left contains mucus and uric acid. 
After washing it, the filter is perforated and the residue 
washed, by means of a wash bottle, into a small test tube, two 
or three drops of sodic hydrate solution are added, it is heated 
and filtered. 

a. The undissolved residue is mucus. 

/3. The filtrate contains the uric acid, which when treated 
with hydrochloric acid separates in crystals which are ex- 
amined under the microscope (§ 6, c). The remainder is dis- 
solved in nitric acid, carefully evaporated to dryness and 
exposed to ammonia, as mentioned in § 6, E, 1, a. If a purple 
violet color is formed, which becomes purple blue on adding 
potassic hydrate, it is absolute proof of the presence of uric 
acid. 

If the residue is immediately treated with sodic hydrate or 
potassic hydrate instead of with ammonia, a purple violet solu- 
tion results, which becomes paler on heating, and at last 
wholly loses its beautiful color. (Distinction from xanthin.) 

The uric acid is easily obtained in finely formed crystals, if 
200 cc. of urine are treated with 5 cc. of hydrochloric acid, and 
left at rest for twelve hours (§ 6, E, 2). 

d. The alcoholic extract of a large quantity of urine is re- 
quired in testing for lactic acid (§ 30, C). 

e. The method described in § 5, D, for the simultaneous de- 



326 AJ^iALYSIS OF THE UBmE. 

tection of kreatinin, xanthin, and urea, gives with certainty the 
desired result. 

f. Oxaluric acid can only be detected by using very large 
quantities of urine (§ 7, E). 

4. Three or four cc. of fuming hydrochloric acid are mixed 
in a test tube with twenty -or twenty-four drops of the urine to 
be tested. If 'U7*oxantJun (indican) is present, the mixture in a 
very short time becomes colored a red violet or intense blue. 
If on account of the minute quantity of uroxantliin present, 
the reaction does not take place, it may often be produced by 
adding a few drops of strong nitric acid (§ 10, lY. c). The test 
with calcic hypochlorite by Jaffs's method (§ 40, lY. c, 2) is also 
very delicate. 

In testing for urohilin we proceed exactly according to § 10, 1, c. 

5. If the urine is colored more or less deeply brown or 
green, etc., if it foams on being shaken, and if a piece of filter 
paper is colored yellow or green on being dipped into it, we 
have reason to test for hile. 

a. A small quantity of urine is poured into a conical-shaped 
glass, and nitric acid containing nitrous acid is added, drop by 
drop, without shaking. If in the lower part of the fluid a color 
is formed which passes through green, blue, violet to red, and 
lastly into yellow, the presence of the bile pigments is indi- 
cated. 

If there are only slight traces of bile pigment present, the 
nitric acid is to be carefully covered with a layer of the urine 
to be tested, or the bile pigment is to be first separated with 
chloroform (§ 28, D, 1 and 2). 

b. In testing for the biliary acids, 400 or 600 cc. are evapo- 
rated on the water bath and the alcoholic extract employed. 
For the process see § 29, under Detection. Pettenkofer's 
test, as stated there, is performed in a porcelain dish. 

If the reaction mentioned does not occur, but the urine be- 
trays the presence of biliary pigment by its color, this may be 
choletelin, the last yellow product which results from the ac- 
tion of nitric acid, etc., on bilirubin. In this case we test 
according to § 28, D, 3, and confirm by the spectroscopic test. 

To detect the biliary acids in normal urine they are to be 
separated with chloroform according to Dragendorff's method 
(§ 29, Detection, 3). 



QUALITATIVE ANALYSIS. 327 

6. If there is any reason to test for sugar : 

a. Fifteen or twenty drops of the urine in question are diluted 
with 4 or 5 cc. of water, i cc. of sodic hydrate is added, and 
then a very dilute solution of sulphate of copper is dropped in. 
If sugar is present, red suboxide of copper separates imme- 
diately on heating, but in the cold only after standing a long- 
time (§ 25, D, 7). 

If the reduction is not well marked, if the suboxide of copper 
remains in solution, the urine is filtered through animal char- 
coal until it is completely decolorized, and is then used for the 
above test. 

The following serve as confirmatory tests : 

a. The potash test. § 25, D, 5. 

/3. The bismuth test. § 25, D, 10. 

y. The indigo reduction test. § 25, D, 6. 

d. The silver reduction. § 25, D, 9. 

6. The fermentation test. § 25, D, 8. 

b. If the reactions given under a are not decisive, if, indeed, 
only traces of sugar are present, it must first be separated in a 
pure form, according to § 25, E, 11. , and the solution obtained 
be finally used for the above reactions. 

7. If the urine has the odor of sulphuretted hydrogen, if it 
colors brown or black a piece of paper moistened with basic 
acetate of lead (§ 34), the presence of sulphuretted hydrogen is 
indicated. 

8. To test the urine for inorganic substances, a portion (80 or 
100 cc.) should be evaporated to dryness and the residue ig- 
nited, as described in § 60. The ash is extracted with water, 
filtered, and tested as follows : 

a. A small portion of it is rendered acid with hydrochloric 
acid, and chloride of barium is added ; a white pulverulent 
precipitate indicates the presence of sulphuric acid. 

b. A second portion is made acid with nitric acid, and a so- 
lution of nitrate of silver is added. A white curdy precipitate 
indicates chlorine. 

c. A third portion is treated with acetate of sodium, acetic 
acid, and a few drops of uranium solution ; a yellowish- white 
gelatinous precipitate indicates j^hosphoric acid. 

d. The rest of the aqueous solution is evaporated to dryness, 
and a small portion of the saline mass heated to redness on a 



328 AJSTALYSIS OF TUB UBINE, 

platinum wire in the inner flame of the blowpipe ; a yellowish 
color of the outer part of the flame indicates sodium. 

e. The rest of the saline mass, obtained as indicated in d is 
dissolved in a few drops of water, and platinic chloride added. 
A yellow crystalline precipitate indicates potassium. 

To test for lithium, which readily passes into the urine on 
being taken internally, the dried saline mass obtained in d is 
next repeatedly treated with absolute alcohol, the alcoholic 
solution is evaporated to dryness, and the residue tested with 
the spectroscope. Salts of lithium give a beautiful bright red 
line between the Frauenhofer lines B and C. 

9. The residue of 8, treated with water, is heated with hydro- 
chloric acid, filtered, washed, and tested as follows : 

a. A small portion of the solution is boiled with a drop of 
nitric acid, and sulphocyanide of potassium is added ; if a red 
color is produced iron is present. 

b. The rest is treated with an excess of acetate of sodium and 
tested for calcium with oxalate of ammonium. 

c. All of the calcium is precipitated, the fluid separated by 
filtration, and ammonia added to the filtrate. A white crystal- 
line precipitate of ammonio-magnesian phosphate indicates the 
presence of magnesium. 

Most of these tests (8 and 9) can be performed with the origi- 
nal urine, filtered if necessary, yet they give clearer and more 
distinct results when the tests are applied to the ash. 

10. In testing for ammoniacal salts, 50 or 100 cc. of urine are 
treated with milk of lime in a flask, in the body of which a piece 
of moistened turmeric paper is suspended from the stopper. If 
ammonium salts are present the paper quickly becomes brown 

(§19)- 

11. The possible presence of iodine is best detected by dis- 
tillation with sulphuric acid according to § 71, C. The distillate 
obtained, after removing the sulphurous acid, may be tested for 
iodine with a few drops of starch paste, and the careful addition 
of chlorine water, or, better still, of red fuming nitric acid instead 
of with the palladium solution (§ 71, C). The smallest traces of 
iodine will give rise to the formation of blue iodide of starch. 

For other methods of testing for bromine and iodine see § 56, 
I. C, 8, 9, and § 71, 2. 

12. In testing for the volatile fatty acids and carbolic acid 



RECOGXITIO:^ OF SEDIMENTS UNDER MICROSCOPE. 329 

large quantities of urine are necessary, and tlie analysis should 
not be undertaken with less than 50 or 60 pounds of urine. For 
the methods see § 9 and § 31. 

13. Benzoic acid is only found in decomposed alkaline urine. 
6 or 8 pounds are requisite to detect it satisfactorily. Benzoic 
acid is best found in fermented diabetic urine. To separate it 
we must proceed exactly as is described in § 32, D. 

14 Inosite has hitherto only been found in cases of Bright' s 
disease and diabetes (§ 27, D). 

15. AUantoin. See § 35, E. 

16. To test for xanthin we require large quantities of urine 
(§5,D). 

17. Leucin and tyrosin have been found in acute atrophy of 
the liver, typhoid fever, small-pox, etc. It is probable that the 
urine then contains, in addition to these substances, valerianic 
acid also. For the methods of detecting see § 37, E. 

18. For nitric acid, nitrous acid, and peroxide of hydrogen, we 
test according to § 21 and § 22. 

19. "We test for oxymandel acid as in § 38 ; it has thus far 
only been found in acute atrophy of the liver. 

20. We test for brenzcatechin according to § 39. 

21. For acetone we test according to § 41. 



II. Eecognition of Sediments under the Microscope. 



If we wish to examine the sediment of a urine, it is neces- 
sary to know first whether the urine in question is fresh, or 
whether it has already stood a long time, and the changes 
which are caused by fermentation have commenced. We there- 
fore test its reaction, let the sediment subside completely in a 
closed vessel, pour off the supernatant fluid, which must be 
examined according to § 87, and place a drop of the sediment 
on a glass slide. If the quantity of urine is small, it is poured 
into a champagne glass and left at rest until the fluid has be- 
come clear. The supernatant fluid is then removed with a si- 
phon, and a drop of the sediment which has collected in the 
apex of the glass is placed on a glass slide. If the quantity of 
urine is large, that of twenty-four hours, it is first allowed to 



330 ANALYSIS OF THE URINE. 

settle in a covered vessel, the clear fluid is then drawn off with 
a siphon, the rest is put into a champagne glass and again al- 
lowed to settle, and we then proceed as before. The drop on 
the slide is next covered with a covering glass and systemati- 
cally examined, by beginning on one side of the specimen and 
pushing it back and forth under the objective until every point 
of it has been in the field of vision. When we have examined 
one specimen, a second is taken, etc.; it is advisable, also, to 
take specimens from different layers of the sediment, since 
some bodies sink more rapidly than others. When it is pos- 
sible, the microscopic examination should be made twice ; first, 
as soon as possible after the urine has been passed, and again 
when the urine has stood twenty-four hours. Calcic oxalate, 
for example, is not usually found in freshly passed urine, but 
first makes its appearance after the lapse of a few hours. We 
increase our magnifying power from 50 or 80 diameters up to 
300 and 400. If the urine has been filtered to separate the 
sediment and the latter is removed from the filter by scraping, 
we must be careful to avoid regarding paper fibres, etc., as con- 
stituents of the sediment. 

A. The Urine has an Acid Reaction. 

1. The tvhole sediment is amo)yhoiis, arranged partly in irregu- 
lar heaps, or in branched mossy rows of very small granules. 
A drop is heated on a glass slide. 

a. If complete solution takes place it indicates the presence 
of urates. (Plate 11. , fig. 1 and 2.) After it has cooled, a drop 
of hydrochloric acid is added, and it is allowed to stand for a 
quarter or half an hour ; the formation of rhombic tables of uric 
acid proves the presence of this substance. (Plate I., ^g. 2.) 

In mosfc cases this sediment consists of a mixture of acid 
urates, and is distinguishnd by a more or less red color. (Plate 
II., fig. 1 and 2.) The sediment is tested chemically, according 
to §44. 

These sediments are very frequently accompanied by uric 
acid and calcic oxalate crystals. (Plate I, fig. 3; and Plate II., 
fig. 4.) 

b. If the sediment does not dissolve on being heated, but 
does dissolve in acetic acid without effervescence, calcic phos- 
phate is probably present. We confirm chemically as in § 46. 

c. If we find in the amorphous sediment small, highly re- 



RECOGNITION OF 8EDIMENT8 UNDER MICROSCOPE. 33I 

fractive, silvery, sliining drops, whicli are soluble in etlier, they 
indicate the presence oifat (§ 33). 

2. The Sediment contains toell-formed Crystals, 

a. Small, shining, perfectly transparent, highly refractive, en- 
velope-shaped, rhombic octahedra, insoluble in acetic acid, are 
calcic oxalate crystals. (Plate I., fig. 3; Plate II., fig. 4, § 45.) 
(300 or 400 diameters.) 

b. Four-sided tables, or six-sided plates of rhombic shape, 
from which spindle- or barrel-shaped crystals are formed by 
the rounding of their obtuse angles, are uric acid. These sedi- 
ments are usually more or less colored. (Plate I., fig. 2 and 3; 
Plate IL, fig. 4; Plate III, fig. 1, § 6, C.) 

We can detect it chemically by the murexid test (§ 6, E, 
1, a). 

If there is doubt about some of the forms, the sediment is 
dissolved in a drop of sodic hydrate solution on a glass slide, a 
drop of hydrochloric acid is added, and the forms which now 
appear are observed. 

Just at the commencement of the alkaline fermentation the 
uric acid crystals, which are more or less dissolved, are fre- 
quently studded with groups of prismatic crystals consisting of 
urate of sodium, upon which again are deposited concentrically 
striped spheres of urate of ammonium. Not unfrequently soli- 
tary crystals of calcic oxalate are found at this time also. 

c. Kegular six-sided tables, which dissolve in hydrochloric 
acid and ammonia, char and burn on heating, and which give a 
precipitate of sulphide of lead when boiled with a solution of 
lead oxide in caustic soda, consist of cystin. (§ 47, Plate III., 
fig. 4) 

The test with nitroprussiate of sodium for cystin is very deli- 
cate (§ 47, C, 8). 

d. Prismatic, often wedged-shaped crystals which sometimes 
lie singly, and sometimes with their pointed ends so placed to- 
gether that they form a more or less complete circle, consist of 
crystallized calcic phosphate (§ 46, 2). 

These crystals are quite soluble in acetic acid. 

e. Heavy, greenish-brown, spherical granules with a stellate 
crystalline structure may consist of ty rosin. Saturating its am- 
moniacal solution with acetic acid precipitates characteristic 
groups of long shining needles (§ 37, B). 



332 ANALYSIS OF THE URINE. 

To confirm its presence the different chemical tests are ap- 
plied, according to § 37, C, 2, 3, 4 

Urine containing tyrosin very frequently contains bile pig- 
ments also. 

f. Hippiiric acid is very rarely met with as a sediment in the 
form of needles or rhombic prisms which are readily soluble in 
hot water (§ 8, B, D). 

3. The Sediment contains Organized Substances, 

a. Spiral bands which consist of fine points and granules ar- 
ranged in rows are mucous coagula, and are often accompanied 
by urates. (Plate II., fig. 2, § 50.) 

These must not be confounded with so-called casts. (See e.) 
(§ 53 ; Plate I., fig. 4, 5, 6.) 

b. Small, strongly contracted and granular bodies, which are 
usually united by their edges into large groups like a coat of 
mail, are mucous corpuscles, (§ 50, Plate II., fig. 3.) 

c. Circular, slightly biconcave disks, which usually appear 
yellow, become swollen strongly on the addition of acetic acid, 
and are more less quickly dissolved by it, are hlood corpuscles, 
(Plate III., fig. 1 and 2.) 

We should pay special regard to the swollen spherical forms, 
as well as to the distorted, angular, and crenated ones (§ 51). 
When blood is present the urine contains albumen. 

d. Bound, pale, faintly granular cells of different sizes, which 
become swollen considerably by acetic acid, lose their granular 
surface and present nuclei of different forms and groupings, are 
pus corpuscles. (§ 52, Plate III., fig. 3.) We cannot distinguish 
these bodies chemically or microscopically from mucous cor- 
puscles. (Plate II., fig. 3.) 

When pus is present, the urine contains albumen. 

The deposited sediment, when pus is present, is changed to 
a thick, tenacious, ropy mass by potassic or sodic hydrate so- 
lution. (Donne's pus test, § 52, B.) 

e. Cylindrical bodies often studded with blood and pus cor- 
puscles and accompanied by epithelial cells and mucous corpus- 
cles are so-called renal casts. (§ 53, Plate I., ^g. 4, 5, and 6.) 

aa. Cylindrical casts whose round nucleated cells are dis- 
tinctly visible through a fine molecular mass are epitJielial casts 
of the tubes of Bellini. (Plate I., fig. 4) 

These forms are usually accompanied by free club-shaped, 



BEGOONITION OF SEDIMENTS UNDER MICROSCOPE. 333 

caudate or spindle-shaped nucleated epithelial cells from the 
ureters, pelvis, and calices of the kidney. (Plate I., ^q. 4) 

bb. Solid cylinders of a granular cloudy appearance are the 
so-called granular renal casts. (Plate I., fig. 6.) 

These cylinders often contain blood and pus corpuscles as 
well as fat drops and granules of fat, also crystals of calcic oxa- 
late and single epithelial cells. 

The sediment, moreover, frequently contains blood and pus 
corpuscles as well as the free epithelal cells mentioned under 
aa. (Plate I., fig. 6.) 

cc. Solid cylinders of very pale transparent character, so that 
we can frequently distinguish them from the surrounding fluid 
only with great difficulty, are the so-called hyaline renal casts. 
(Plate L, fig. 5.) 

Their recognition is rendered easier if a solution of iodine in 
iodide of potassium or a solution of fuchsin is added to the 
specimen whereby these bodies assume a yellow or red color. 

We frequently find intermediate forms between bb and cc, by 
the hyaline casts assuming a more or less granular appearance, 
owing to overlying fat drops, pus corpuscles, and finely granu- 
lar masses. 

Every specimen of urine containing albumen must he carefully ex- 
amined for these different bodies. "We should choose a power of 
180 or 200 diameters. 

f. Epithelial cells of different forms according to their source. 

aa. Pavement epithelium. Roundish, long, or polygonal nu- 
cleated cells from the large and small labia, the vagina, the 
female urethra, bladder, pelvis of the kidney, and calices. (Plate 
I., fig. 4, 5, 6 ; Plate 11, fig. 1, § 50, 2.) 

bb. Cylindrical and oval epithelium from the lower layer of 
the mucous membrane of the bladder, etc. 

cc. Ciliated epithelium from the uterus. 

The addition of a solution of iodine in iodide of potassium or 
of a solution of fuchsin renders all of these forms more distinctly 
visible under the microscope. 

g. Fermentation spores and mycelium accompany sediments 
of urates, free uric acid, and calcic oxalate in commencing acid 
fermentation, but occur especially in diabetic urine which has 
undergone fermentation. 

aa. The fermentation spores are small nucleated cells which 



334 ANALYSIS OF THE URmE. 

increase by budding, and thus form simple or branched rows. 
(Plate II., ^. 1, 2, 4.) 

bb. Mycelium often forms a thick network which may coyer 
the whole field. (See page 189, fig. 5.) 

h. Short fine rods which move briskly here and there or with 
a serpentine motion are vihriones ; they are commonly seen in 
feebly acid or alkaline urine wdth a high power (§ 55). 

i. Spermatozoa are recognized by their tadjDole-like shape 
(§ 54). 

k. Masses of Cancer. (Plate III., fig. 5 and 6.) 

1. Sarcina ventrictdi, Goodsir. Yery rare. Its characteristic 
form does not admit of its being easily mistaken. (Page 189, 
fig- 6.) 

B. The Urine is Alkaline. 

1. The Sediment contains Crystals. 

a. Combinations of the vertical rhombic prism, which resem- 
ble a coffin lid in shape, are soluble in acetic acid, and on heat- 
ing with a solution of sodic hydrate evolve ammonia, are crystals 
of ammonio-magnesian phosphate. (§ 46, 1 ; Plate II., fig. 3 and 5.) 

If calcic oxalate should occur with these, the sediment is 
treated with a drop of acetic acid on a glass slide ; the crystals 
of magnesium phosphate will dissolve, wdiile the calcic oxalate 
will remain behind in its envelope-shaped crystalline form. 

b. Spherical oj)aque masses Avhich appear like thorn apples 
with peculiar, prominent, fine points, but also in glandular con- 
glomerations consisting of small, curved, club-shaped bodies, 
are urate of ammonium. (§ 44, 3; Plate II., fig. 5.) 

2. The Sediment contains Amorp)hous Classes. 

In an alkaline urine these almost always consist only of calcic 
phosphate (§ 46, 2). 

3. The Sediment contains Organized Bodies. 

Besides mucus, blood and pus corpuscles, etc., we find here 
fermentation spores and mycelium, infusoria, and confervoe 
(§ 55, page 189, fig. 5). In an alkaline urine pus is changed to a 
ropy slimy mass (§ 52, B). 

§ 89. Peesekvation of Ueinaey Sediments. 

As in many cases it may be of interest to preserve urinary 
sediments as microscopic objects, the following short introduc- 



RECOGNITIOJ>f OF SEDIMENTS UNDER MICROSCOPE. 335 

tion for tliat piirpose may find mention here. First of all it is 
necessary to separate the sediment from the urinary fluid, as 
the urine soon undergoes decomposition, and, therefore, organ- 
ized bodies especially are easily destroyed. The sediment is, 
therefore, allowed to settle in a champagne glass, the urine as 
far as possible is drawn off with a siphon, and the sediment is 
then washed three or four times by decantation with the preser- 
vative fluid, in wdiich Ave wish to enclose it later. Two methods 
are open to us : we may either put the washed sediment into 
a small bottle, fill it with the preservative fluid, and write the 
contents on a label, or we may place the sediment on a glass 
slide and preserve it as a finished preparation under a cover- 
ing glass hermetically sealed. 

Of the different preservative fluids proposed for this pur- 
pose glycerine solution,^ creosote and wood spirit solution,t 
dilute alcohol, J Tarrant's fluid,§ etc., are best fitted for the va- 
rious epithelial cells, renal casts, pus and mucous corpuscles, 
spores, uric acid, urates, calcic oxalate, etcil Ammonio-magne- 
sian phosphate is best preserved in water to which a little 
ammonia has been added. Yery dilute acetic acid is selected 
for cystin. Crystalline sediments, with the exception of am- 
monio-magnesian phosphate and calcic oxalate, may be pre- 
served in Canada balsam, but they must first be very completely 

" Glycerine solution is obtained by diluting commercial, tliick, syrupy gly- 
cerine with equal parts of camphor water. It forms an excellent preserving 
fluid. 

f Creosote and wood spirit solution is obtained as follows : Three drams 
of creosote are mixed in a mortar with six ounces of wood spirit, and powdered 
chalk is added until the whole forms a thin pulp, which is then diluted with 
sixty-four ounces of water while being rubbed well together. A few pieces of 
camphor may also be added. The mixture is then allowed to stand two or 
three weeks in a closely covered glass, being frequently stirred. At last the 
clear fluid is poured off, filtered, and preserved in a well-stoppered bottle. 

I Rectified spirit is diluted with from two to eight times its quantity of water. 
It is less suitable for microscopic preparations, since it is difiicult to hermeti- 
cally seal preparations preserved in alcohol. 

§ A mixture of equal volumes of very thick mucilage, glycerine, and a cold 
saturated solution of arsenious acid. 

li [Reviser's Note. — An excellent preservative fluid for the organized sediments 
is a solution of the acetate of potassium to which a little carbolic acid has been 
added. The acetate of potassium solution should have a sp. gr. of between 
1-050 and 1-060, and should contain 4 to 5 cc. of deliquesced carbolic acid to the 
liter of solution.] 



336 AJ^ALTSIS OF THE URINE. 

washed and carefully dried. The following procedure is the 
simplest : The well-washed sediment is placed on a glass slide 
and allowed to dry thoroughly in the sun or over sulphuric 
acid ; it is then moistened with a drop of oil of turpentine, the 
greater part of which is again allowed to evaporate. A drop 
of Canada balsam is now placed upon it, it is gently warmed, 
any air bubbles present are removed with a needle, and it is 
covered with a previously warmed covering glass. By careful 
pressure the excess of balsam is forced out, and after a few 
days it dries and forms a perfectly tight border around the cov- 
ering glass. For still greater security the edge may be covered 
with asphalt varnish, which is an article of commerce, and may 
be readily applied with a camel' s-hair brush. 

To preserve sediments in a fluid we proceed as follows : A 
drop of the sediment suspended in the preservative is placed 
on a glass slide and a covering glass previously breathed upon 
is carefully placed over it with a pair of forceps, taking care 
that no air bubbles are included under it. The excess of fluid 
is then removed by gentle pressure, carefully absorbed by filter 
paper, and the preparation laid aside a few minutes to allow 
the very last of the fluid to evaporate. We now place the 
preparation under the microscope to see that everything is 
right, and then proceed to hermetically seal it. The covering 
glass is first fastened to the slide by means of wax. The wick 
of a thin wax taper is sharpened into a chisel shape, then 
heated to the melting point over a spirit lamp, but not until it 
burns, and then, while the wick is held horizontally, it is quickly 
drawn along the edge of the covering glass. In this process 
drops of wax must not be allowed to fall oiF, but only just 
enough to perfectly fill the furrow between the covering glass 
and glass slide, and the whole border of wax should not be 
more than 2 mm. wide. With a little practice the wax may be 
as evenly laid on as fluid with a brush. When the wax bedding 
is finished, it is covered with asphalt varnish, which may be 
easily applied with a hair pencil, so as to cover the wax bed 
2 mm. beyond each edge ; we have thus a border about 6 mm. 
broad, which surrounds the preparation. In applying the as- 
phalt we must proceed with care, and see that we cover all of 
the corners and edges well, and that no air bubbles have been 
included anywhere ; this we can best determine by means of a 



QUANTITATIVE ANALYSIS. 337 

hand lens. We should be especially careful not to make this 
first layer of asphalt too thick, since it then hardens only on 
the surface, still remaining fluid beneath and easily being drawn 
under the covering glass and thus spoiling the preparation. I 
have lost many preparations in this way. If after twenty-four 
hours the first layer of varnish has become solid, a second 
thicker one is applied over it, when the preparation may be 
labelled. 

The glass slides should be 48 mm. long and 28 mm. broad. 
Protectors, 10 mm. broad, should be glued on to both ends with 
mucilage or silicate of potassium varnish, and at the same time 
they should carry the labels. These protectors are to be 
recommended very highly, since the covering glass is then 
never in danger when the preparations are packed one upon 
another. The finished preparations should never be placed 
on their edge, since they then more readily become leaky, but 
they should always be laid flat in a box lined with cloth. The 
process described here is applicable not only to urinary sedi- 
ments, but also to many other microscopic preparations."^ 

III. QUANTITATIVE ANALYSIS. 
§90. 

If we have obtained a satisfactory knowledge of the urine 
under examination qualitatively, according to § 87 and § 88, we 
proceed to determine the constituents quantitatively. Unfor- 
tunately, however, we do not yet possess simple and accurate 
methods for determining quantitatively all of the bodies which 
occur, therefore we must content ourselves with estimating the 
most important of the normal and abnormal constituents. 

1. Estimation of the Quantity of Urine Passed in a Given Time 
(§57). 

According to the purpose which we have in view, we either 
determine the amount of urine for twenty-four hours, or for a 
shorter time. The amount should be stated in cubic centime- 
ters (§ 57). 

"" Very thoroTig-li instruction in this subject can be found in Welker's Aufbe- 
waJtrung microscopischer Objecte, Giessen, 1856 ; also in Reinliard's Das Micro- 
scop und scin Oebrauch fur den Arzt, Leipzig and Heidelberg. 
22 



338 ANALYSIS OF THE URINE. 

2. Estimation of the Specific Gravity (§ 58). 

In most cases the determination of the sp. gr. can be made 
with the urinometer, § 58, 1. But if greater accuracy is desir- 
able, we use the method of weighing, § 58, 2 and 3. 

The statement of the sp. gr. is rendered more complete by a 
simultaneous statement of the temperature of the urine. 

3. Determination of the Water and of the Total Solids (§ 59). 

10 or 15 cc. of urine are evaporated on the water bath in a 
weighed porcelain crucible exactly according to § 59, and the 
residue is dried in the air bath at 100^ until it no longer loses 
weight. After subtracting the weight of the crucible we obtain 
the amount of solid constituents, and if we subtract this from 
the amount of urine taken, it gives us the amount of water 
in the urine. 

Much more accurate results are obtained when the evapora- 
tion of the urine is performed in the apparatus figured in § 59, 
2, fig. 17. The ammonia which is liberated by the decompo- 
sition of the urea when the urine is evaporated is calculated as 
urea, and this is added to the residue found by weighing. 

4 Determination of tJie Non-volatile Salts (§ 60). 

10 cc. of urine are evaporated to dryness in a weighed plati- 
num crucible, and the residue is ignited as described in § 60. 

If we wish to determine the constituents which are soluble 
in water separately from those which are insoluble, we boil the 
weighed residue with Avater, filter, wash, evaporate the aqueous 
extract to dryness in a weighed platinum crucible, ignite gently, 
and weigh. The weight of salts soluble in water subtracted 
from the whole quantity of non- volatile bodies found gives as the 
difference the amount of salts insoluble in water. 

5. Determination of the Coloring Alatter by VogeVs Method, 
This process is carried out exactly as described in § 61. 

6. Determination of tJie Urea. 

A. The Urine contains no Albumen. 

50 cc. of urine are mixed with 25 cc. of a cold saturated solu- 
tion of caustic baryta and nitrate of barium (§ 65, B, 3), and 
the resulting precipitate filtered through a dry filter. 

The filtrate obtained is divided into two portions. 

a. One portion is made very feebly acid with dilute nitric 
acid, 15 cc. are measured off with a pipette, corresponding to 
10 cc. of urine, and it is treated with a standard solution of 



QUANTITATIVE ANALYSIS. 339 

mercuric nitrate from a Molir burette drop by drop until a dis- 
tinct, permanent, whitish cloudiness appears. The number of 
cc. used up to this point gives the correction for chloride of so- 
dium and is subtracted from the number of cc. of mercury so- 
lution used under b (§ 65, D, 3, at the end). (Eautenberg's 
method.) 

b. The second portion of the filtrate is not rendered acid, but 
15 cc.=10 cc. of urine are also measured off with a pipette, and 
the urea is determined by the standard solution of mercuric 
nitrate, § 65, C. This is added from a burette until a drop of 
the mixture saturated with carbonate of sodium on a watch 
glass gives a distinct yellow color. If the mixture remains 
white, there is still some uncombined urea present, and more 
mercuric solution must be added. The result of the first 
should be confirmed by a second test ; every cubic centimeter 
of the mercuric solution used, after subtracting those obtained 
under a, corresponds to 10 mgrm. of urea. 

For the principle, preparation of the solutions, etc., see § 65. 

Coi^redions. 

aa. The Urine contains more than tico j)er cent, of Urea. 

If more than 30 cc. of the mercuric solution have been em- 
ployed for the 15 cc. of the urine mixture, before testing the 
mixture with carbonate of sodium, we must add a quantity of 
water equal to half that of the mercuric solution in excess of 30 
cc. which has been used (§ 65, D, 1). 

bb. The Urine contains less than tiuo loer cent, of Urea. 

If less than 30 cc. of the mercuric solution have been used for 
the 15 cc. of the urine mixture, 0*1 cc. must be subtracted for 
every 5 cc. less than 30 cc. which have been used, and the re- 
mainder calculated for urea (§ 65, D, 2). 

cc. The Urhie contains one to one and a half per cent, of Chloride 
of Sodium. 

If we wish to obtain perfectly accurate results, the chlorine 
must first be removed by a standard solution of nitrate of sil- 
ver. The urea in the filtrate is then determined by the mer- 
curic solution as usual, account being taken of the dilution which 
has been caused by the nitrate of silver solution (bb). (§ 65, 
D,3.) 

The method of Eautenberg described in § 65, J), 3, at the 
end, gives nearly as accurate results. (See page 239.) 



340 ANALYSIS OF THE URINE. 

dd. The Urine contains carhonate of ammonium (§ 65, D, 5, b). 

A measured volume of urine, which has been completely 
precipitated by baryta solution, is subjected to distillation, and 
the ammonia which is set free is received in a measured volume 
of standard sulphuric acid (§ 65, D, 5, b). Each cubic centime- 
ter of the saturated acid corresponds to 11 '32 mgrm. of ammo- 
nia or 20 mgrm. of urea. 

The undecomposed urea is determined as usual in the resi- 
due freed from ammonium salts. 

B. The Urine contains Albumen. 

The albumen in a definite quantity of urine is coagulated 
as in § 65, D, 4, filtered, and the urea, after precipitating 
the phosphates with baryta solution, determined as usual 
(§ 65, C). 

For clinical purposes the method of Knop-Hiifner (§ 65), 
with hypobromite of sodium, is also to be highly recommended. 

7. determination of the Chlorine (§ 66). 

5 or 10 cc. of urine are treated with 1 or 2 grm. of pure nitre, 
evaporated to dryness in a platinum evaporating dish, and care- 
fully heated until the organic bodies are completely decom- 
posed. The white saline residue is dissolved in water, accu- 
fately neutralized with nitric acid, and the chlorine estimated 
with the solution of- nitrate of silver according to § 66, C. 

Each cc. of the silver solution corresponds to 6*065 mgrm. of 
chlorine or 10 mgrm. of chloride of sodium. 

8. Determination of the Phosphoric Acid (§ 67). 

a. Estimation of the Total Amount. 50 cc. of urine are treated 
with 5 cc. of an acid solution of acetate of sodium, heated on 
the water bath, and then the phosphoric acid is determined 
with a standard solution of acetate of uranium. During the 
addition it is frequently tested by adding a drop of the mixture 
to a solution of ferrocyanide of potassium in the manner re- 
commended in § 67, C, until a slight excess of uranium is in- 
dicated by a faint red color. Each cubic centimeter of the 
uranium solution used corresponds to 5 mgrm. of phosphoric 
acid (§ 67, C, a). 

b. Determination of the Phosphoric Acid combined tvith Alkalies. 
50 cc. of urine are rendered alkaline with ammonia, the earthy 
phosphates are filtered off after a few hours, the precipitate is 
washed, and the phosphoric acid is estimated in the whole filtrate 



QUANTITATIVE ANALYSIS. 341 

after adding 5 cc. of the acetate of sodium solution as explained 
in a. 

Each cubic centimeter of the uranium solution which was 
used indicates 5 mgrm. of phosphoric acid which were in com- 
bination with the alkalies. The quantity thus obtained sub- 
tracted from the whole quantity previously determined gives as 
a difference the phosphoric acid combined with the earths. 

9. Determination of the Free Acids (§ 68). 

50 cc. of urine are treated drop by drop with a solution of 
sodic hydrate standardized with pure oxalic acid, until the acid 
reaction has wholly disappeared and a drop placed on litmus 
paper neither makes it blue nor red. Each cc. of the solution 
of sodic hydrate used corresponds to 10 mgrm. of oxalic acid. 

10. Determination of the Sulphuric Acids (§ 69). 

100 cc. of urine are heated to boiling after the addition of 20 
or 30 drops of hydrochloric acid, and a standard solution of 
chloride of barium, each cubic centimeter of which indicates 10 
mgrm. of sulphuric acid, is added drop by drop until the neutral 
point has been reached (§ 69, A), or until a slight excess of 
barium is indicated by sulphate of potassium in a filtered speci- 
men. If 12 cc. have been required up to this point, but no re- 
action with sulphate of potassium has taken place when 11 cc- 
have been used, the true amount lies between 11 and 12 cc. 
We immediately add 11 cc. of the chloride of barium solution 
to a new quantity, heat to boiling, and complete the estimation 
exactly according to § 69, C 

11. Determination of the Sugar (§ 70). 

In this estimation the urine must be diluted so that it con- 
tains at most I per cent, of sugar. 10 cc. of the standard copper 
solution are then measured off, diluted with 40 cc. of water, 
heated to boiling, and the dilute urine added until all of the 
copper has been reduced, and a filtered specimen, after being 
rendered acid by hydrochloric acid, no longer gives the copper 
test with sulphuretted hydrogen. In most cases a proper di- 
lution is attained by mixing 5 cc. of diabetic urine with 95 cc. 
of water. However, the dilution must depend on the greater or 
less quantity of sugar in the urine. 

The volume of urine employed for the complete reduction 
contains exactly 50 mgrm. of diabetic sugar. If now we have 
diluted the urine, for example, to twenty times its volume before 



342 AJS'ALTSIS OF THE UBUSTB. 

testing, we must divide 20 x 5=100 by tlie number of cubic centi- 
meters used in order to obtain the percentage of sugar in the 
urine (§ 70, C). Knapp's method is equally accurate (§ 70, 2). 

The estimation of sugar optically with the polariscope is more 
quickly accomplished (§ 70, 3). 

Yery satisfactory results are also obtained by the difference 
of the specific gravity before and after fermentation. (Manas- 
sein's method, § 70, 5.) 

12. Determination of the Albumen (§ 75). 

The process is carried out just as described in § 75. 

13. Determination of the Uric Acid (§ 73). 

200 cc. of urine are treated with 5 cc. of hydrochloric acid of 
1*11 sp. gr., covered and left at rest from twenty-four to thirty- 
six hours in a cool place at a temperature of 10° or 15° C. (in 
most cases twenty-four hours are sufficient) ; the fluid is then 
drawn off with a siphon, and lastly the crystals are collected on 
a small dried and weighed filter. After washing (the drops 
which come away should not have an acid reaction) it is dried at 
100^ C. and weighed (§ 73). 

14. Determination of the Kreatinin. 

We proceed exactly according to § 74, C. 

15. Determination of the Calcium (§ 76, L, C). 

200 cc. of urine are treated with ammonia, the resulting pre- 
cipitate dissolved in as little acetic acid as possible, and the 
calcium precipitated with oxalate of ammonium. When the 
fluid has become perfectly clear it is drawn off with a siphon, 
the calcic oxalate is collected on a filter, washed, ignited, and 
titrated with hydrochloric acid and sodic hydrate solution, as 
described in § 76, C. 1 cc. of saturated hydrochloric acid cor- 
responds to 10 mgrm. of CaO, or 18*45 mgrm. of SOaO^POs. 

16. Determination of the Magnesium (§ 76, II. 1). 

a. The fluid obtained in 15 is united with the wash water, 
and the magnesium is precipitated by ammonia as ammonio- 
magnesian phosphate. After twelve hours the clear fluid is 
drawn off with a siphon, the precipitate collected on a filter, 
washed with water containing ammonia, ignited, and weighed 
(§ 76, II. 1). Or the phosphate of magnesium is dissolved in 
acetic acid, and the magnesium determined by titrating the 
phosphoric acid contained in the precipitate, as described in 
§ 76, II. 2. 



QUANTITATIVE ANALYSIS, 343 

b. 200 cc. of urine are precipitated with ammonia, the earthy 
phosphates which separate are collected on a filter after a few 
hours, washed with water containing ammonia, dried and ig- 
nited just as we have described in § 76, II. 1, b. The quantity 
of phosphate of calcium obtained subtracted from the quantity 
of earthy phosphates found gives as a remainder the quantity 
of phosphate of magnesium (2MgOP05) which was present. I 
prefer this second process to the one described under a. 

17. Determination of tJie Ammonia (§ 77). 

20 cc. of urine are mixed with milk of lime and placed in the 
apparatus described and figured in § 77, C, beside a measured 
volume of standard sulphuric. acid, and the non-saturated por- 
tion of the acid, after forty-eight hours, is titrated back with 
sodic hydrate of known strength (§ 77, C). 

18. Determination of the Iron (§ 72). 

200 cc. of urine are evaporated to dryness, ignited according 
to § 60, until all of the carbon is consumed, dissolved in hy- 
drochloric acid, the oxide of iron which is formed is reduced 
by boiling with sulphite of sodium, allowed to cool, diluted to 
60 cc, and the iron present determined by a solution of perma- 
ganate of potassium, whose strength has been ascertained just 
before using it by a solution of oxalic acid or ferrocyanide of 
potassium (§ 72). 

19. Determination of the Potassium and Sodium* 
We proceed as in § 79. 

20. Determination of the Fat 
According to § 82. 

21. Determination of the free Carbonic Acid. 
We proceed exactly as in § 80. 

22. Determination of the Iodine. 
After the method given in § 71. 

23. Determination of the Total Nitrogen contained in the Urine 

(§81). 

24. Determination of the Indican (§ 84). 

25. Determination of the Oxalic Acid in Solution (§ 85). 

26. Determination of Biliary Acids (§ 83). 



344 AI^ALTSIS OF THE URINE. 

IV. PRACTICAL GUIDE FOR APPROXIMATE ESTIMATIONS. 

§91. 

Althougli we are able by means of tlie different Yolumetric 
methods to ascertain with certainty and rapidity the quantity of 
very many constituents of the urine, still cases occur in which 
the physician wishes to determine immediately whether a urine 
contains more or less of a certain constituent than has been 
the case at another time. But since it is not necessary to give 
a special guide for approximately estimating every constituent, 
the two methods employed by Beneke ^ may serve as examples 
of others. 

1. Estimatioyi of the Earthy Phosphates hy the llethod of Beneke, 

The earthy phosphates are known to be held in solution in 
the urine by the free acids, and separate when the urine be- 
comes alkaline. 

If, therefore, we saturate the free acid of the urine with any 
alkali, we obtain a precipitate if the urine contains earthy 
phosphates. According to the amount of the earthy phos- 
phates in solution there will be either no cloudiness at all or 
only a very slight one, and sometimes a larger, sometimes a 
smaller precipitate will result. These differences are charac- 
teristic enough to enable us to draw an approximate conclusion 
as to the quantity present. 

If we always use for such estimations a vessel of the same 
diameter, which at a certain mark contains exactly 15 or 20 
cc, we can, as the large number of experiments performed by 
Beneke show, soon distinguish quite definitely different de- 
grees of cloudiness or j^recipitation. If we first establish a 
scale for the different degrees of cloudiness which arise, and, 
secondly, determine by accurate analysis the actual quantity 
corresponding to each degree of the scale, we have all of the 
conditions which are requisite for the performance of such an 
analysis. 

For estimating the earthy phosphates seven degrees of 
cloudiness are distinguished by Beneke, and the amount cor- 

"■ Beneke, Zur Pliysiologie und Pathologie des phosphorsauren und oxal- 
sauren Kalks, QSttingen, 1850. 



PRACTICAL GUIDE FOR APPROXIMATE ESTIMATIONS. 345 

responding to these was determined according to the method 
described in § 76. 
Beneke marks : 

1. With 0, a urine which, after being boiled in a test tnbe 
and treated with 5, 10, or 15 drops of a sodic hydrate solution 
(one part of sodic hydrate in twelve parts of water), showed no 
cloudiness, but remained as clear as before. 

2. With J, a urine which when similarly treated showed a 
slight opacity. 

3. With 1, a urine which, treated in the same way, gave a 
strong opacity, yet of such a kind that objects behind the glass, 
as, for example, the frames and borders of a window, could be 
distinguished through it. 

4. With 1 \, a urine which, after the addition of sodic hydrate, 
gave so great a degree of cloudiness, yet still somewhat opa- 
lescent, that an object behind the glass could scarcely be dis- 
tinguished. 

5. With 2, a urine which becomes very turbid and loses its 
opalescence. 

6. With 2\, a urine which yields a considerable precipitate 
of earthy phosphates a few seconds after adding the sodic hy- 
drate. 

7. With 3, a urine which immediately gives a large precipitate. 

8. With 3 to 4, finally, a urine which separated a very large 
quantity of earthy phosphates immediately after the addition of 
sodic hydrate. 

It is easy to see that we may become so familiar with the dif- 
ferent degrees of cloudiness by frequent repetition of this sort 
of test, that a specimen may readily be classified according to 
the scale. Cases occur, how^ever, in which the appearances do 
not agree with any one of the given numbers; such may be 
designated with sufficient accuracy by saying J-, J, 1], I3, etc. 

If the urine is alkaline any sediment of earthy phosphates 
which is present is equally divided, one portion of the urine is 
then boiled, and, according as the alkaline reaction is weak or 
strong, only a little or none of the solution of sodic hydrate is 
added. If the urine contains albumen, it is coagulated by boil- 
ing, filtered, and the filtrate then tested for phosphates. 

Beneke has found by accurate analysis that the scale he gives 
corresponds to the following quantities in an ounce of urine *. 



346 



ANALYSIS OF THE UBINE. 



Urine marked contains about 0-100 or 150 grm. of earthy phosphates. 



i " 


" 0-250 " 0-300 




1 


" 0-400 " 450 




U " 


" 0-550 " 0-600 




3 


" 0700 " 0-750 




2i 


" 0-850 " 0-900 




3 


" 1-000 " 1-050 




3 to 4 " 


•' 1-000 " 1 300 





"We can thus easily reckon approximately how much earthy 
phosphates are passed with the urine in twenty-four hours. 

2. Estimation of the Calcic Oxalate by Benekes 3IetJiod. To esti- 
mate the quantity of calcic oxalate approximately, Beneke used 
a method similar to the one just described, which, in brief, is as 
follows : In testing for calcic oxalate it is necessary, on each 
occasion, to allow a portion of the urine under investigation to 
stand twenty-four hours in a test tube. If at the end of this 
time a sediment has formed in the lowest part of the glass, the 
clear fluid is poured off and one of the last drops examined un- 
der the microscope. This test must not be omitted, even if no 
distinct cloudiness is observed in the specimen. If we find a 
sediment of urates, the drop is warmed on the glass slide to 
dissolve the urates, and the calcium phosphate is removed by 
a drop of acetic acid, when the calcic oxalate will remain behind 
alone in most cases. By operating in this way, by always exam- 
ining only one drop of the sediment on the slide, and by cover- 
ing the drop with a thin covering glass, we Avill be able to decide 
as to the quantity of calcic oxalate present. 

To get a better idea, Beneke has here, also, distinguished the 
different quantities with numbers : 

Urine marked contains no calcic oxalate, 

± " very little calcic oxalate. 

1 " little 
H " a moderate amount of calcic oxalate. 

2 '* considerable " " 
2^ " much 

3 to 4 " an exceedingly large quantity of calcic oxalate. 

Since it is quite apparent that each person must make such a 
scale for himself, I content myself with having brought forward 
these two methods of Beneke, similar to which others may 
be easily arranged for albumen, uric acid, sulphuric acid, etc. 
Such approximate estimates, however, can lay no claim to great 
accuracy. 



ANALYTICAL EXPERIMENTS. 347 

ANALYTICAL EXPERIMENTS. 

§92. 

I. Table for Estimating the Total Solids from the Specific Gravity 
(§ 59, 3). 



SPECIFIC GKAYITT. 


SOLIDS FOUKD BY 
WEIGHII^G. 


SOLIDS CALCULATED 

BY MULTIPLYING 

BY 0-233. 




PER THOUSAND. 


PER THOUSAND. 


1-0160 


37-4 


37-28 


1-02-60 


62-0 


60-58 


1-0154 


35-1 


35-88 


1-0261 


60-2 


60-81 


1-0213 


48-6 


- 49-63 


1-0230 


56-4 


53-59 


1-0230 


56-0 


53-59 


1-0225 


49-3 


52-42 


1-0240 


54-1 


55-92 


1-0257 


60-4 


59-88 


1-0275 


63-9 


64-07 


1-0275 


64-2 


64-07 


1-0217 


48-5 


50-56 


1-0223 


52*15 


51-96 


1-0140 


31-08 


32-62 


1-0236 


56-64 


54-98 


1-0133 


30-87 


30-99 


1-0134 


31-06 


31-22 


1-0238 


57-09 


55-45 


1-0250 


60-47 


58-25 


1-0164 


37-26 


38-21 


1-0135 


33-35 


31-45 


1-0210 


48-54 


48-93 


1-0137 


32-55 


31-92 


1-0085 


19-16 


19-80 


1-0110 


24-96 


25-63 




Average 




1-0200 


46-59 


46-52 



348 ANALYSIS OF THE URINE. 

From these determinations we find tliat by dividing tlie mean 
quantity of solid constituents found in 1,000 grm. of urine by 
the last three decimals of the mean sp. gr., we obtain the quo- 
tient 0*23295, for which we may conveniently put down the num- 
ber 0'233, as Haser suggests. By multiplying with this quotient 
the three last decimals of the sp. gr. carried out to four places 
of decimals, we obtain the figures given in the third column, 
whose difference from those obtained by gravimetric analy- 
sis may be seen in the above table. If, however, the specific 
gravity has been determined only to three decimals, the second 
and third figures multiplied by 2 '33 give, approximately, the 
amount of solid matters in 1,000 parts of urine. 

II. Determination of the Chlorine (§ Q>Q). 

The comparative analyses were carried out according to the 
following methods : 

a. 5 cc. of urine were evaporated with nitre, the organic mat- 
ters destroyed by ignition, and the chlorine determined by a 
solution of nitrate of silver. 

b. 5 cc. of urine were heated with different quantities of per- 
manganate of potassium solution (four grm. to the liter), and the 
chlorine in the filtrate titrated with nitrate of silver solution. 

c. 5 cc. of urine were diluted with 10 cc. of water, and the 
chlorine directly titrated with a solution of nitrate of silver. 

\st Series. Mixed uinne of twenty-four hours. 

^ 7'5 per thousand of NaCl. 

1. According to a there were found \ T'o " " 

( 7-6 

2. According to h, 

5 cc. of urine with 10 cc. of permanganate solution 8 8 per thousand of NaCl. 
5 cc. " '' 20 cc. " " 8-8 

5 cc. " " 30 cc. " " 8-5 

■ 5 cc. " '♦ 40 cc. " '* 8.2 

3. According to c there were found 9 "2 to 9*4 ** " 
Id Series. The mixed twenty-four hours' urine. 

^ , -,. X XI n , < 6 1 per thousand of NaCl. 

1. According to a there were found ] n.-i .* ^< 

2. According to b, 

„ . . -, ^^ „ , . ( 64 per thousand NaCl. 

5 cc. of urine with 20 cc. of permanganate solution j ,^ ,, ,, 



ANALYTICAL EXPERIMENTS. 349 

5 cc. of urine with 30 cc. of permanganate solution -S ^'^ P®^ thousand NaCl. 

{ 6-3 

(A slight excess of permanganate must be destroyed by a few drops of oxalic acid solulion.) 

3. According to c there were found Q'Q to 6 '8 per thousand of NaCl. 

3c? Series. Concentrated morning urine. 

1. According to a there were found \ ^'^ P^^ thousand of NaCl. 

I 4-6 

2. According to b, 

5 cc. of urine with 50 cc. of permanganate solution \ ^'^ ^^^ thousand of NaCl. 

( 4 J 
(A slight excess of permanganate must be decomposed by a few drops of oxalic acid solution.) 

( 5 8 per thousand of NaCl. 

3. According to c there were found ■< 5 '7 " " 

( 5.7 

The procedure a, therefore, yields the most accurate results. 

III. Determination of the Phosphoric Acid. With oxide of 
uranium solution (§ 67). 

The titration was performed according to the directions given 
above for every 50 cc. of urine ; the gravimetric estimation, on 
the other hand, for every 100 cc, according to the ordinary 
method and with the observance of all requisite precautions. 
The ammonio-magnesian phosphate before ignition was mois- 
tened with a few drops of a concentrated solution of nitrate of 
ammonium, and thus the phosphate of magnesium obtained 
perfectly white. It gave the following results : 

Volumetric Analysis." Gravimetric Analysis. 

100 cc. 0-1302 \^'IT.^ 

] 0-1299 

100 cc. 0-2352 0-2342 

100 cc. 0-1389 -i^'I^^L 

< 01410? 

100 cc. 0-1312 j 01318 

( 0-1324 

IV. Determination of the Sidphuric Acid ( § 69). 

The sulphuric acid in each 100 cc. of urine was determined 
by weighing and by the volumetric method, and the following 
results obtained : 



350 ANALYSIS OF TEE URINE. 

Gravimetric. Volumetric. 

0-139 grm. SO3 0'128 grm. SO 3 

0-182 " " 0177 " *' 

0-274 " *' 0-270 " *' 

0139 '* " 0187 '' " 

0-235 " *' 0-238 " " 

V. Determination of Sugar (§ 70). 

1. 0*4: grm. of pure grape sugar was dissolved in 20 cc. of 
urine and diluted to 100 cc. ; the urine consequently contained 
2 per cent, of sugar. 12 '3 cc. were required to reduce 10 cc. of 
the copper solution. There were found, therefore, 

5x5 

=:2-03 per cent. 

12-3 

0*6 grm. of grape sugar was dissolved in 20 cc. of urine and 
diluted to 100 cc. ; the urine, therefore, contained 3 per cent, of 
sugar. 84 cc. were required to reduce 10 cc. of the copper so- 
lution. There was found, therefore, 

5x5 

= 2*97 per cent. 

8-4 ^ 

2 grm. of grape sugar were dissolved in 20 cc. of urine and 
diluted to 400 cc. ; the urine then contained 10 per cent, of 
sugar. 10*5 cc. were required, to reduce 10 cc. of the copper 
solution. There was found, therefore, 

20x5 

=9-5 per cent. 

10-5 ^ 

2. Comparative experiments with diabetic urine carried out 
by the methods of Fehling, Knapp, and optically with the 
Yentzke-Soleil apparatus, gave the following results : 



a. According to Fehling's method 

" Knapp's " 

By circumpolarization 

b. According to Fehling's method 

'' Knapp's '' 

By circumpolarization 



3-59 per cent. 
3-68 '' 
2-40 " 

3-67 '' 
3-47 '' 
2-10. '' 



ANALYTICAL EXPERIMENTS. 351 

VI. Determination of the Kreatinin (§ 74). 

0-8938 grm. of kreatinin, the purity of which was proved by 
estimating the nitrogen, were dissolved in 2 or 3 cc. of water 
and diluted to 160 cc. with absolute alcohol. Each 50 cc. of this 
solution, in which 0*2793 grm. of kreatinin was dissolved, were 
measured off and precipitated by adding J cc. of an alcoholic so- 
lution of chloride of zinc of 1'195 sp. gr. After standing forty- 
eight hours in a cool place the resulting precipitate was care- 
fully collected on a weighed filter, and dried at 100° C, the 
filtrate first obtained always being used for collecting the pre- 
cipitate on the filter. The washing with absolute alcohol was 
only commenced when the mother liquor had completely run 
off. When dried at 100^ the following results were obtained : 

1. 0*2793 grm. of kreatinin gave 0*4438 grm. of kreatinin chlo- 
ride of zinc corresponding to 99*2 per cent. 

2. 0*2793 grm. of kreatinin gave 0*4429 grm. of kreatinin chlo- 
ride of zinc corresponding to 99*0 per cent. 

3. 0*2793 grm. of kreatinin gave 0*4439 grm. of kreatinin chlo- 
ride of zinc corresponding to 99*2 per cent. 

As an additional measure an estimation of the nitrogen was 
made with the kreatinin chloride of zinc obtained from the 
alcoholic solution : 0*3453 grm. dried at 100" C. gave 0*0798 
grm. of N; corresponding to 23*1 per cent of N, while the cal- 
culation required 23*21 per cent. 100 parts of kreatinin chlo- 
ride of zinc dried at 100° C. correspond, therefore, to 62*44 per 
cent, of kreatinin. 

From the above calculations it appears, therefore, that the 
estimation of kreatinin with chloride of zinc nearly equals in 
accuracy the estimation of potassium with platinic chloride. 

VII. Determination of the Albumen (§ 75). 

Double analyses by weight were very carefully made wdth 
clear filtered urine containing a solution of albumen. 
1. a. 100 cc. gave 1*130 grm. of albumen dried at 100° 0. 



b. 


100 cc. 




1*107 


a. 


100 cc. 




0*624 


b. 


100 cc. 




0*616 


a. 


100 cc. 




0*600 


b. 


100 cc. 




0*588 



VIII. Determination of the Calcium (§ 76). 

0*222 grm. of calcic phosphate were converted into carbonate 



352 ANALYSIS OF THE UBINE. 

according to § 76, 1, and then dissolved in 20 cc. of hydrocliloric 
acid, 1 cc. of which corresponded to 10 mgrm. of CaO. 10'2 cc. 
of sodic hydrate solution of corresponding strength were re- 
quired for titrating back; consequently 20 — 10'2 = 9*8 cc. of 
hydrochloric acid were saturated by the lime. 

The 0'222 grm. of calcic phosphate contained, therefore, 0*098 
grm. = 44'14 per cent, of CaO. The gravimetric estimation 
gave 44*20 per cent, of CaO. 

Each 100 cc. of the same urine treated by this method gave 
a percentage of 0*0420 and 0*423 of lime. 

IX. Determination of the Ammonia (§ 77). 

The sulphuric acid employed in these experiments contained 
0*5304 grm. of SO3 in 10 cc, corresponding to 0*22542 grm. of 
NH.. 22*1 cc. of solution of sodic hydrate were required to 
saturate 10 cc. ; 1 cc. of sodic hydrate solution, therefore, cor- 
responded to -'-IW-^ = 0*0102 grm. NH,. 

1. 10 cc. of urine were directly treated with milk of lime. 
After forty-eight hours the NH3 evolved corresponded to 0*8 cc. 
of the sodic hydrate solution. Consequently the urine con- 
tained 0*081 per Cent, of NH^ 

2. 40 cc. of the same urine were freed from the coloring and 
extractive matters by 40 cc. of the mixture of the acetate and 
basic acetate of lead solutions. 20 cc. of the clear filtrate, cor- 
responding to 10 cc. of urine, after forty-eight hours had evolved 
the same quantity of NII3 ; 0*8 cc. of the sodic hydrate solution 
was saturated. 

After another forty-eight hours the two specimens had evolved 
no more NHo. 

3. To 10 cc. of the same urine 0*2343 grm. of chloride of 
ammonium dried at 100' C. were added. At the end of the 
experiment 14*1 cc. of the sodic hydrate solution were required 
to saturate the 10 cc. of sulphuric acid. The NII3 evolved cor- 
responded, therefore, to 22*1 - 14*1 = 8 cc. of sodic hydrate 
solution. 

The 10 cc. of urine alone corresponded to 0*8 cc. of sodic hy- 
drate solution ; there remains then 8*0 - 0*8 = 7*2 cc. of sodic 
hydrate solution for the chloride of ammonium added. 7*2 cc. 
of sodic hydrate correspond to (7*2 x 0*0102) = '07344 grm. NH3, 
and this (17 : 53*46 = 00*07344 : x) = 0*2309 grm. of chloride of 



ANALYTICAL EXPERIMENTS. 353 

ammonium. Thus 0*2309 grm. were found again for the 0*2343 
grm. added. 

4. 10 cc. of another specimen of urine were treated directly 
with milk of lime. The XH^ evolved corresponded to 1*25 cc. 
of sodic hydrate. So that the urine contained 0*1275 per cent, 
of A^Hc 

After another forty-eight hours no more ^Hg was evolved. 

5. 10 cc. of the same urine were treated with 0*1744 grm. of 
chloride of ammonium. After the end of the experiment 15*4 
cc. of sodic hydrate were required to saturate the 10 cc. of SO.. 
The i^Hg evolved, therefore, corresponded to 22*1 — 15*4 = 6*7 
cc. of sodic hydrate. The 10 cc. of urine alone corresponded 
to 1*25 cc, and thus there remained 6*7 — 1*25 = 5*45 cc. of 
sodic hydrate for the chloride of ammonium added. 5*45 cc. 
correspond to (5*45 x 0*0102) = 0*05559 grm. of NH,, and this to 
0*1747 grm. of chloride of ammonium. Instead of the 0*1744 grm. 
added, then 0*1747 grm. of chloride of ammonium were found. 

23 



PART SECOND. 



THE SEMIOLOGY OF HUMAN URINE ; 

OR, 

THE ESTIMATION AND SIGNIFICANCE OF THE CHANGES OF 

THIS FLUID : 

TOGETHEK WITH A 

GUIDE TO THE EXAMINATION OF URINARY CALCULI AND 

OTHER URINARY CONCRETIONS, 

WITH SPECIAL EEFERENCE TO THE PUEPOSES OF THE PRACTISING PHYSICIAN. 

BT 

JULIUS YOGEL. 



INTEODUCTION. 

The study and analysis of the urine has been regarded from 
the earliest times as of great assistance in recognizing and form- 
ing an opinion concerning diseased conditions. Nevertheless, 
before the chemical and microscopic methods of examination 
were perfected, the real value of this branch of science was 
slight, and the inspection of the zirine, often misused by charlatans 
to deceive an ignorant public, consequently for a long time fell 
into discredit both with scientific physicians and the educated 
portion of the public."^ "With the improvement of organic chem- 
istry and the general use of the microscojDe, uroscopy first as- 
sumed a scientific character, and no one now doubts that it is 
entitled to form an important and essential part of semiology and 
diagnosis. Many important diseases are distinctly recognized 
and accurately determined only by an examination of the urine : 
thus the different forms of diabetes, most kinds of nephritis, etc., 
many conditions dangerous to the health, can only be warded off 
by observing the changes of the urine, such as the risk of the 
formation of a calculus, etc. 

The aid which an examination of the urine renders the physi- 
cian in reference to diagnosis, prognosis, and treatment may be 
of two kinds. An examination of the urine enables us to draw 
conclusions : 



■^Unfortunately this metliod of inspecting urine practised by charlatans 
threatens to crop out again at the present time. The author has had frequent 
opportunity to convince himself of this ; indeed, it is not merely uneducated 
persons belonging to the lowest classes of society who allow themselves to be 
deceived by such "marvellous doctors," but also people who belong to the higher 
and especially "educated" masses. Under such circumstances it doubly be- 
comes the duty of physicians to point out to the public what aid a scientific 
study of the urine can furnish in the diagnosis, prognosis, and treatment of dif- 
ferent diseases. 

357 



358 INTRODUCTION. 

1. As to tlie general conditions of the economy, the relations 
of metamorphosis, character of the blood, the digestion, etc. 

2. As to certain local diseases of organs belonging to the uro- 
poetic system. 

In the following pages we shall as far as possible consider 
both of these points equally. 

Moreover, the examination of the urine may sometimes give 
information concerning special facts and processes which pos- 
sess a certain importance for the physician. Thus we are fre- 
quently able from the mere inspection of the urine to determine 
whether a patient has a fever or not. From the odor or the 
color of the urine we know that certain articles of food or medi- 
cine have been taken, for examj)le asparagus, oil of turpentine, 
rhubarb, etc. From the appearance of spermatozoa in the 
urine we know that a masturbation or coitus has taken place ; 
from the presence of albumen in the urine we can conclude 
under certain circumstances that the patient is dropsical ; or 
when the urine contains biliary coloring matters that jaundice 
exists, etc. The crafty physician makes use of such indications 
to gain the confidence of his patient in his knowledge or to re- 
tain it ; but the scientific physician will avail himself of them 
cautiously and without ostentation, since any misuse of such 
means stamps him as a charlatan in the eyes of his colleagues 
and of the public. 

In many cases an examination of the urine is of great im- 
portance to therapeutists, since it proves whether certain sub- 
stances which a patient has used as medicine are eliminated 
again with the urine or not. In the latter case the physician 
is cautioned that by a continued use of many medicines he 
may readily produce a so-called cumulative action in the system 
which is dangerous, as is the case with nitre, digitalis, strychnia, 
etc. In the former case, on the other hand, he will be prompted 
to continue the agent, or even to increase the dose, when it is 
desirable to keep the system to a certain degree saturated with 
it for a long time, so that it may have its complete effect slowly 
and gradually, as with iodide of potassium, alkaline carbonates, 
and the like. The importance of examining the urine for such 
purely therapeutical j)urposes has not been hitherto sufficiently 
valued in practice. Its application, however, will surely in- 
crease in proportion as the analytical processes necessary to 



INTBODUGTION. 359 

carry it out, now difficult and incomplete, are further perfected, 
simplified, and rendered easy for the physician — a problem 
whose solution the author Avould most earnestly recommend to 
those chemists who are interested in the subject. 

If the science of urinary examination in reference to the 
above point has been hitherto neglected, there are, on the 
other hand, other points in regard to which its value has been 
overestimated. Many special facts will be mentioned later in 
this connection. One erroneous opinion, however, which is 
based on an imperfect knowledge of the nutritive changes in 
disease and upon an ontological way of regarding single forms 
of disease not yet discarded by all pathologists, deserves men- 
tion and a refutation, because it and the conclusions drawn 
from it have a very great range and are widely spread, and 
have even appeared anew in recent works on these subjects. 
It is, the opinion that the different forms of disease are charac- 
terized by a definite condition of the urine which corresponds 
to each. This statement is only true for a very few diseases, 
in which a certain condition has received its name from a char- 
acteristic condition of the urine. It is natural that the urine 
in albuminuria should contain albumen, in lisematuria blood, 
in glycosuria sugar, in oxaluria oxalic acid, etc. ; if this were 
not the case, we should not be justified in giving this name to 
the disease. In other forms of disease we only very rarely find 
any specially characteristic condition of the urine; and when 
recently it has been several times asserted that the urine, for 
example, in typhoid fever, pneumonia, etc., has possessed a cer- 
tain composition or qualities, such observations, as a rule, 
rest on insufficient data or the investigations have been made 
in certain stages of these diseases only. 

Examinations of the urine in the above diseases in which they 
have been made in great number and in all stages of the disease 
show, as will be proved later, that the condition of the urine in 
all acute diseases changes with the progress of the disease, with 
a certain degree of regularity. And that this change in the con- 
dition of the urine ordinarily depends less on the special nature 
of the sickness, especially its local phenomena, than upon cer- 
tain general conditions of the body, such as the intensity of the 
fever, the state of the appetite and digestion, that is, upon the 
greater or less amount of food taken. This is also true of 



360 INTRODUCTION. 

clironic diseases in wliicli acute exacerbations occur, as is often 
the case. For example, tlie wide-spread idea that the amount 
of urea in the urine in Bright's disease is diminished is untrue 
to this extent : that in febrile forms of this disease, just as is 
the rule in all fevers, an increase of the urea is observed. 

Therefore, it appeared better to consider in the following 
pages only the general semiology of the urine, since the special 
semiology of this fluid, that is, the description of the composi- 
tion of the urine in individual diseases, is best left to the con- 
sideration of each disease, that is, to special pathology. 

To render more easy the general study and the solving of 
certain questions, the following pages have been divided into 
two principal divisions and several subdivisions. 

The first division discusses the qualitative changes of the 
urine including the sediment. It contains four sub visions : 

I. Changes in color, appearance, and odor of the urine. 
II. The chemical reaction of the urine and its significance. 
III. The occurrence of unusual or abnormal constituents in 

the urine. 
lY. Urinary sediments. 

The second division comprises the quantitative changes of 
the urine : the increase and diminution of the normal consti- 
tuents. 

It is subdivided into two large groups : 

I. Quantitative changes of the urine which can be determined 
without chemical analysis, and which, on account of their easy 
detection, are especially important to the physician. 

II. Quantitative changes which require a quantitative chem- 
ical analysis for their demonstration. 

A guide to the examination of urinary calculi and other uri- 
nary concretions is added as an appendix. 

Those who desire to study more minutely the changes of the 
urine which occur in disease, especially in regard to their di- 
agnostic significance and the therapeutic indications which they 
give the physician, are referred to my work on the diseases of the 
Iddneys (including the changes in the urine which occur in gen- 
eral diseases) in. the Handbuch der speciellen Patliologie und Ther- 



INTRODUCTION. 361 

apie, Band 6, edited by Yircliow, and published by F. Enke in 
Erlangen. 

Since the author had in view especially the needs of the phy- 
sician, it appeared best, owing to the necessity of as condensed 
a statement as possible, to communicate the results of many 
labors on human urine during the last few years only so far as 
they were of interest not merely to chemists and physiologists 
but to the physician. But to satisfy those who wish to inform 
themselves somewhat more in detail than the space here per- 
mits on many points, especially as to questions which are still 
suhjudice, the literature which contained further information in 
regard to them was referred to. 

Moreover, to avoid repetition, all which has already been 
mentioned in the first part has been omitted, and we have only 
referred to the sections concerned, or to the numbers of the 
pages. 



DIVISION FIEST. 

QUALITATIVE CHANGES OF THE URINE, INCLUD- 
ING URINARY SEDIMENTS. 

I. CHANGES IN THE COLOR, APPEARANCE, AND ODOR 
OF THE URINE. 

The clianojes of the urine which belonsj under this head are 
naturally the most easily detected ; but of themselves alone 
they rarely lead to positive diagnostic and semiotic conclusions. 
Usually they only serve as hints and guides to a further inves- 
tigation of the urine by other means. Therefore, the mere in- 
spection of the urine without using other additional methods of 
investigation is of relatively little value to the physician. 

§ 93. Color of the Urine. 

The color of the urine is due to the coloring matters, whose 
nature and origin, in spite of numerous investigations, has thus 
far not been completely explained. For what is known on this 
point see § 10. We shall only speak of those points here Avhich 
have an importance to the medical practitioner. (Compare 
§122.) 

The color of the urine is an important sign which sometimes 
gives the practitioner valuable indications for judging of the 
condition of a disease ; but still more frequently it may serve 
to give him a general idea of it, and to point out to him the 
direction for his further investigations. 

As practitioners we must distinguish between normal and ab- 
normal color of the urine. 

1. The normal color of the urine is yellow, with a greater or 
less admixture with red. It varies from almost colorless (like 
water), through yellow, to red and reddish brown. 

363 



364 SEMIOLOGY OF HUMAN URmE. 

These different shades of color of normal urine may be clas- 
sified in the following principal groups : 

Pale — colorless to straw yellow."^ 

Normal — gold to amber yellow, t 

High color — reddish yellow to red.J 

Darlc — with a brownish tint, dark beer-color to blackish. § 

A pale urine contains little coloring matter, little urea, and, as 
a rule, also only little solid constituents (except diabetes mel- 
litus). It is seldom very acid, frequently neutral or alkaline. 
It is observed in persons in perfect health after copious drinking 
(urina potus), in many who are suffering from chronic diseases 
(ansemia, chlorosis, diabetes), as well as frequently in convales- 
cents from^ severe acute diseases. The existence of a pale 
urine is an almost absolute indication to the physician that the pa- 
tient in question does not suffer from a severe acute febrile disease, 
and a urine which continues to be very pale for a long time 
always indicates a certain degree of anaemia (oligocythsemia). 

Normally colored urine only warrants the negative conclusion, 
that no disease exists which from its nature is characterized 
by a very pale or very high-colored urine. 

High-colored urine is generally concentrated, abounds in solid 
constituents (has, therefore, a high specific gravity), is rich in 
urea, and usually very acid. It occurs in cases in which the 
secretion of water by the kidneys is diminished, while the secre- 
tion of the other constituents of the urine is normal or even in- 
creased. It, therefore, occurs in perfectly healthy persons after 
eating hearty meals (urina chyli), or when they have perspired 
freely and drunk little, as after vigorous exercise. It occurs in 
almost all febrile diseases, and becomes, therefore, an important 
sign to the physician. In hectic fevers especially it is often a 
surer indication than the pulse and the temperature in deciding 
as to the intensity of a febrile increase of metamorphosis. 

Darh urine, as a rule, indicates that an abnormal pigment is 
mixed with the urine, the determination and significance of 
which requires a more careful investigation. 

Occasionally it is desirable to determine the color of a urine 

* Plate IV., fig. 1 and 2. 
f Plate IV., fig. 2 to 4. 
i Plate IV., fig. 5 and 6. 
§ Plate IV., fia:. 7 to 9. 



CHANOES m COLOB, APPEABANCE, AND ODOB, 365 

more accurately tlian according to the above general categories. 
We then proceed according to § 61, and make use of the con- 
siderations mentioned in § 122 for drawing the conclusions 
therefrom. 

Heller has given still another method for approximately de- 
termining the quantity of the ordinary urinary coloring matter 
named by him urophaein.^^ A little concentrated English sul- 
phuric acid is poured into a beaker and about double its quan- 
tity of the urine to be tested is added. If the mixture is 
quickly stirred it becomes colored more or less dark brown or 
tarry black. From the intensity of the color we decide as to 
the amount of urophaein present. Ziegier states that the most 
intense color is produced by this test in cases of chronic de- 
generation of the liver, especially cirrhosis of the liver, and 
he uses this urophein test as an aid in the diagnosis of this 
disease. 

In many cases the color of the urine depends on different 
pigments which are present at the same time — soluble pigments 
which are dissolved in the urine, and insoluble ones which ad- 
here to the sediments. It is, therefore, well to filter the urine 
in order to be better able to decide as to the part which the 
different pigments play in coloring the urine. 

2. Abnormal color of the urine results from the presence of 
unusual coloring matters. 

These unusual urinary pigments may be divided into two 
groups : 

a. Essential abnormal colors of the urine, which are formed 
within the organism as the result of certain pathological pro- 
cesses, and, therefore, have an important significance for the 
practitioner. 

b. Accidental abnormal colors, which get into the body from 
without, in the food, drink, or medicine, and are eliminated 
again with the urine, merely passing through the economy. 

The most important abnormal colors of the urine are : 
a. The Essential, caused 

1. By Blood Pigments. These form very different shades ac- 
cording as the blood red is dissolved, in combination with the 

■^Compare Ziegier, Die Uroscopie am Krankenbette, Erlangen, Ferd. Enke, 
1861, S. 24, et seq. 



3G6 SEMIOLOGY OF HUMAJS' URINE. 

blood corpuscles, decomposed, unclianged, or present in the 
•urine in greater or less quantity. The shades of color which 
are thus produced may vary from blood red (bright garnet red) 
to brown, brownish black, or even to an inky black. For the 
detection and the significance of this blood coloring matter in 
the urine, see § 99 and § 100, and the cases 11, 12, and 13 in § 134. 

2. By Biliary Pigments. The color of this urine is yellowish 
green or brownish green. For the details see § 102. 

3. By Indican (uroxanthin) and its products of decomposition, 
uroglaucin and urrhodin. See § 10, page 67, et seq.^ 

Uroxanthin rarely has any apjDreciable influence on the color 
of the urine ; it is only in those cases in wdiich, with a defi- 
ciency of urophaein (urobilin), a large amount of uroxanthin is 
present, that the urine assumes a lemon-yellow color (in cholera 
and affections of the spine). To demonstrate the presence of 
uroxanthin, however, a chemical process is always necessary, as 
has been described already on page 71, C. 

According to Baumstark,t indican belongs with hippuric 
acid, tyrosin, and the biliary acids in the chemical series of so- 
called " aromatic compounds," and is probably formed in the 
liver especially. 

According to Jaffe's observations the small quantity of indi- 
can normally present in the urine is increased by a meat diet ; 
it is diminished to a mere trace by a diet containing little nitro- 
gen ; according to Jaffe and Hoppe-Seyler, it is considerably in- 
creased in carcinoma of the liver, and also in cholera, according 
to Jaffe and Wyss. 

According to Jaffe, diseases which bring about an obstruction 
of the small intestine (strangulated hernia, incarceration, etc.) 
very considerably increase the secretion of indican with the 
urine (ten or fifteen times the normal amount) ; obstruction of 
the large intestine increases it less, as experiments on dogs 
proved. In purulent peritonitis also, probably on account of 
the diminished motion of the small intestines, the indican is in- 

•" Heller, in liis Arcliiv fiir Cliemie und Microscopie, 1852, S. 121, ct seq. 
M. Jaffe (Pfluger's ArcMv, ill., p. 448, et seq.). Ibid., Ueber den Ursprung des 
Indicans im Harn, Centralbl. fiir d. medic. Wissenschaften, 1872, p. 2. Ibid., 
Ueber die Ausscbeidung des Indicans unter pbysiolog. u. patbolog. Verbaltnis- 
sen, ibid., p. 481, et seq., 497, et seq. 

f Berliner klin. W ochensclir. , 1873, Nr. 4 



CHANGES IN COLOB, APPEARANCE, AND ODOR. 367 

creased. Also in certain diarrhoeas (cholera and cholera mor- 
bus), but not in catarrh of the large intestine, accompanied by 
discharges at the same time from the large intestine only. Fever 
appears to have no essential influence on the amount of indican 
in the urine. 

J. Eosenstern^ found the quantity of indican in the urine 
essentially increased in Addison's disease. 

According to Heller f and his scholars, the amount of indican 
which can be detected in the urine is, in some degree, a measure 
of the amount of excitation of the nervous system, especially 
of the spinal cord (?). It is said to be increased in urina spastica, 
after too frequent coitus, onanism, etc., also in every irritation 
of the urinary organs, every acute and chronic disease of the 
kidney (nephritis, Bright's disease, perinephritis, etc.), and in 
many general diseases also, as typhoid fever, intermittent fever, 
cholera, and uraemia. 

According to observations which R. Lawson (compare § 122) 
made in Jamaica, the urine of the inhabitants of the tropics is 
usually rich in indican, even under normal circumstances. 

Uroglaucin and urrhodin, products of the decomposition of 
uroxanthin,^: occur only rarely in the urine, when it has under- 
gone decomposition in the bladder, with the production of a large 
amount of carbonate of ammonium (in cystitis and Bright's 
disease). It may then, however, give rise to very striking colors 
of the urine (green, blue, and violet.) Uroglaucin has a blue 
color, urrhodin a red color, and from a combination of these 
two with each other, and with the ordinary yellow urinary color- 
ing matters many various shades of color may be produced. 

Thus the urine may become green (greenish to beautiful 
grass green) when blue uroglaucin occurs in a yellow urine. It 
appears blue when the normal (yellow) coloring matter is want- 
ing and uroglaucin predominates ; violet, when uroglaucin and 
urrhodin are present together; reddish, wdien the latter pre- 
dominates. 

Uroglaucin and urrhodin usually form sediments, and, there- 
fore, we must filter such a urine. Moreover, urrhodin dissolves 

* Vircliow's Archiv, 1872, Ivi., p. 27, et seq. 
f Ziegler, loc. cit., p. 28. 

X S. Kletzinsky in Heller's Arcliiv, 1853, p. 414, and Sclierer in Ann. der 
Cliemie und Pharmacie, Band 90, Heft 1, p. 120. 



368 SEMIOLOGY OF HUMAN UBINE. 

in ether with a beautiful carmine red color, uroglaucin dissolves 
in boiling alcohol with a beautiful blue color. 

4. By urocrythrin, which sometimes, when dissolved in the 
urine, gives it a red color, sometimes when precipitated with 
sediments of uric acid and urates gives them a brick-red or rose- 
red color. Compare page TS."^* 

The urine presents a very peculiar appearance in the majority 
of persons who suffer from melanotic cancer. Of the normal 
color when passed, it gradually becomes brown or even black 
when exposed to the air. This dark color appears still more 
quickly when oxidizing substances have been added, as nitric 
or chromic acid. This proceeds from a peculiar substance 
characteristic of melanotic cancer — melanogen. This peculiarity 
of the urine may be rendered serviceable for the diagnosis of 
melanotic cancer which is concealed in the internal organs, as, 
for example, in the liver. t 

b. Accidental Various coloring matters which enter the body 
as constituents of food, drink, and medicines may be eliminated 
again with the urine and color it. We have very numerous in- 
vestigations on this point, t which, however, are less important 
to the physician than to the physiologist and chemist. 

There are two coloring matters which we may speak of here 
which are also of interest to the physician, since they form 
constituents of medicines frequently used, and which often pass 
into the urine and may resemble urine colored by biliary color- 
ing matter or more especially by blood. These pigments are 
rliiiharl) and senna. Each may color the urine brownish or even 
a deejD blood red. Both can be readily distinguished from the 
color due to blood by chemical means, however. Urine which 
is colored by them on the addition of mineral acids becomes 
brighter, and light yellow, while urine containing blood is not 
made clearer by the acids, but in fact becomes rather darker. 

After taking santonin, also, the urine receives a color similar 
to that produced by biliary matters (saffron yellow or greenish). 
It may be recognized from the fact that on the addition of an 

* Heller in his ArcMv, 1853, p. 391, et seq. 

f For details seeEiselt, Prager VierteljahrescLr., 1858, S. 190, et seq., u. 1862, 
S. 26, et seq. Bolze, ibid., 1860, S. 140, et seq. Pribram, ibid., 1865, S. 16, etseq. 

X Compare the investigations of Kletzinsky in Heller's Arcliiv f. Chemie und 
Mikr., 1852, p. 184, 211, 338. 



CHANGES IN COLOB, APPEARANCE, AND ODOR. 369 

alkali tlie yellow or greenish color, according to tlie amount of 
santonin }3resent, beomes cherry red or purplish red.^ 

After the use of carbolic acid or tar the urine at times as- 
sumes a blackish color. (Compare page 74.) 



§ 94. Odor of the Urine. 

The odor of the urine has no great importance for the physi- 
cian. Many substances which give the urine a peculiar odor en- 
ter the economy from without, like the accidental coloring mat- 
ters described in the previous section, and are separated again 
with the urine. Their presence may be serviceable to the phy- 
sician as an indication that patients have taken certain articles 
of food or medicine. In this way the urine acquires a peculiar 
odor after asparagus has been eaten, a peculiar one (like violets) 
when oil of turpentine has been taken, or when it has simply 
been inhaled in large quantity. We may discover the odors of 
saffron, cubebs, etc., in the urine. 

It has been asserted by French pathologists (De Beauvais 
and others) that the peculiar odors of asparagus, oil of turpen- 
tine, etc., do not appear in the urine in organic diseases of the 
kidney. However valuable this means of diagnosis might have 
been in cases of albuminuria in which the other symptoms left 
it doubtful whether a merely functional disturbance or an or- 
ganic lesion of the kidney existed, I would, after some experi- 
ments of my own, advise that it be accepted with caution. I 
have found twice, for example, that the urine had the characteris- 
tic odor of asparagus and oil of turpentine in cases of albumi- 
nuria, when later the autopsy showed at least a partial organic 
disease of the parenchyma of the kidney. 

But normal urine has a specific odor which Heller referred 
to the coloring matter of the urine (urophaein), but which pro- 
bably depends on various odorous matters, since Stadeler suc- 
ceeded by distilling the urine in obtaining several volatile acids 
from it (phenylic, taurylic, damaluric, and damolic acids). (Com- 
pare § 9.) A preponderance of one or the other of these would 
probably modify the odor of the urine. 

The sense of smell is peculiarly affected by a urine which 

* Walter G. Smitli, Dublin Quart. Journ., c, p. 263, et seq. 

u 



370 SEMIOLOGY OF HUMAN URmE. 

contains much carbonate of ammonium, and the " urinous odor " 
of patients comes chiefly from this source. 



§ 95. Transpakency of the Urine. 

The urine is either clear or cloudy. Slight turbidities form 
a so-called cloud (nubecula), larger ones after standing a long 
time deposit as a precipitate, and form a sediment. All turbi- 
dities of the urine consist of solid particles which are not dis- 
solved but are only suspended in it. They are either already 
contained in the fresh urine, or form in it a longer or shorter 
time after it is passed from the bladder. 

A normal specimen of urine is always clear or at most has 
only a very slight degree of cloudiness. Distinct turbidity of 
the urine always allows us to conclude that there is some abnor- 
mal condition, and must, therefore, arouse the attention of the 
physician. But the significance of the turbidity only becomes 
clear, when we have ascertained its nature. (For further details, 
see Division lY. under Urinary Sediments.) 

II. CHEMICAL REACTION OF THE URINE. 

§ 96. 

Normal urine almost always has an acid reaction ; that is, it 
colors blue litmus paper red. Sometimes, however, its reaction 
is neutral or even alkaline ; in the latter case it renders I'ed lit- 
mus paper blue. 

It is most convenient in testing the reaction of urine to 
use a blue litmus paper, which has a very slight red tint. 
This serves equally well for detecting an acid as well as an 
alkaline reaction, since it is rendered more red by acid and 
deep blue by alkaline urine. It is, moreover, very sensitive. 
It is prepared by allowing an aqueous tincture of litmus to 
stand until it becomes slightly acid, and its intense blue color 
has assumed a reddish tint. Ordinary smooth writing paper is 
dipped in this tincture and dried in the shade. 

Sometimes urine is met with which has both an acid and an 
alkaline reaction ; that is, at the same time it slightly reddens 
blue litmus paper and blues slightly reddened paper. (Amphi- 



CHEMICAL REACTION OF THE URINE. 371 

genous reaction of Heller, or better, amphoterous reaction of 
Bamberger.) 

This paradoxical phenomenon is probably to be explained 
as follows : "When acid phosphate of sodium is neutralized 
by ammonia, a compound results (ammonio-sodic phosphate) 
which has the property of giving off ammonia when it is 
warmed and the pressure on it is diminished, while acid phos- 
jDhate of sodium remains. If, now, ammonia is develoj^ed by 
the decomposition of urea in a urine naturally acid from the 
presence of acid phosphate of sodium, it may be unequally dis- 
tributed in the fluid and render certain portions alkaline, or it 
may form an ammoniacal atmosphere aboye the fluid by which 
red litmus paper is made blue, while other portions of the same 
urine still contain acid phosphate of sodium, and, therefore, 
redden blue litmus paper. In the same manner we often ob- 
serve that a specimen of urine which is commencing to evolve 
ammonia, but which still has a slightly acid reaction, has on its 
surface a pellicle of crystalline ammonio-magnesian phosphate, 
which according to its chemical properties cannot exist in an 
acid fluid.* 

The chemical reaction of the urine gives the 23hysician sev- 
eral useful indications, and is, moreover, a test very easy to 
perform. It is, therefore, a valuable sign in semiology ; and in 
order to render its importance clear we must study this sub- 
ject further. 

Normal urine has an acid reaction. It is not yet positively 
known on what acid this reaction of the urine depends. It is 
probable that it depends only in the rarest cases on the pres- 
ence of a free acid (compare page 6 and § 11), but, as a rule, 
rather on the acid salts ; indeed chiefly on the acid phosphate 
of sodium, and, perhaps, at the same time in many cases, on 
acid urates, hippurates, lactates, etc. 

H. Baysson,t however, believes that the acid reaction of the 
urine does not depend on acid phosjDhates of the alkalies, but 
upon uric, carbonic, and hippuric acids, since uric and hippuric 

" See further concemin;^ tlie so-called amplioterous reaction : W. Heintz, 
Journ. f . prakt. Cliemie, 1872, \i., p. 274, ct seq. 

f Etude sur les causes de la reaction acide de I'urine normale cliez I'liomme et 
de sa variation, Journ. de I'anat. etplijsiol., par. Ch. Robin, 1872, t. viii., p. 383, 
et seq. 



372 SEMIOLOGY OF HUMAN URINE. 

acids are not capable of decomposing neutral phospliate of so- 
dium at ordinary temperatures. 

There are, however, two essentially different ways in which 
the acid reaction of the urine may be lost or even changed to 
the alkaline. 

1. Carbonate of ammonium may be formed in the urine after 
it is secreted ; the urine then becomes neutral if the quantity of 
carbonate of ammonium is small, alkaline when it is greater. 
This development of carbonate of ammonium is caused by a 
decomposition of urea, which under certain circumstances be- 
comes converted into carbonate of ammonium by absorbing 
water. 

1 equivalent of urea C2 H4 Nj O2 
4 '' *' water H4 O4 



C, H3 N, Oe 

= 2 equivalents of carbonate of ammonium = 2 (CO2 + NH4O). 

This conversion of urea into carbonate of ammonium is 
caused by the presence of a ferment. 

It was formerly the opinion that the mucus of the urinary 
passages constituted this ferment. Eecent investigations, how- 
ever, make it probable that it consists of microscopic germs, 
which decompose the urea by their development in the same 
way that yeast decomposes sugar in the alcoholic fermentation. 
Since the spores of this ferment are contained everywhere in 
the air on account of their extreme minuteness, they can very 
readily get into the urine. (Compare pages 7, 9, and 188.) 

Under favorable conditions the urine may become alkaline 
while still within the urinary passages ; it is then alkaline when 
passed. 

The urine thus becoming ammoniacal within the urinary pas- 
sages has a very great practical importance, because it may be 
followed by very bad results : irritation of the mucous mem- 
brane of the urinary passages, blenorrhoea and even gangrene, 
formation of urinary concretions and ammonaemia. It is, there- 
fore, very important to the physician to prevent it as much as 
possible and to remove its cause. Various recent observations 
have shown that these spores may enter the bladder on a 
catheter which is not perfectly clean, and to which the above- 
mentioned ferment may adhere. In the bladder they develop 



CHEMICAL REACTION OF THE UUINE. 373 

further and cause tlie decomposition of urea there.^' Tlie prac- 
tical rule follows, therefore, that every catheter must he^nost care- 
fully cleaned hefore leing used. 

Again, the alkalinity may appear only after the urine has been 
passed ; it then has an acid reaction immediately after being 
passed and becomes alkaline only after a time. Almost every 
specimen of urine becomes alkaline in a longer or shorter time, 
but in normal urine this alkalinity occurs very late, at any rate 
not before twenty-four hours have elapsed. When, therefore, 
urine is evacuated in an alkaline state, or if it is acid when 
passed and becomes alkaline within twenty-four hours after- 
ward, we may conclude that there are circumstances present 
which favor decomposition of the urea, and the physician is jus- 
tified in drawing diagnostic conclusions from this circumstance. 

But one circumstance is to be taken into consideration which, 
if it is overlooked, may lead to error. When urine which has 
already become alkaline is added to normal urine, the latter 
undergoes the ammoniacal fermentation much quicker than it 
otherwise would. This is the case when the urine is kept in a 
vessel which contains any remains of ammoniacal urine. When 
the physician, therefore, would draw conclusions from the fact 
of urine having become rapidly alkaline, say within twenty-four 
hours, he must be certain that it was kept in a perfectly clean 
vessel; he must, therefore, see that the chamber vessels and 
urine glasses of the patient are not merely emptied, but are also 
washed out, so that every trace of the ferment is removed. 

Urine which has been rendered alkaline by carbonate of am- 
monium colors red litmus paper blue, but after the paper has 
become dry and the carbonate of ammonium has volatilized, while 
the acid salts of the urine remain behind, the blue litmus paper 
becomes red again. Moreover, a glass rod moistened with hydro- 
chloric acid and held over such a urine develops a cloud of 
chloride of ammonium. This fact is important, because it 
serves to distinguish the alkalinity of the urine caused by car- 
bonate of ammonium from that resulting from other causes. 

V. Feltz and E. Eitter, professors at the academy of medicine 
in Nancy,t have arrived at the following results from their in- 

*S. Fischer, Berliner Min. Wocliensclir. , 1864, 2. TeufPel, ibid. 16. 
f Etude experimentale sur ralcalinite des urines et sur rammoniemie, im 
Joum. de I'anat. et physiol., par Ch. Robin, 1874, Nr. 3, p. 311, et seq. 



374 SEMIOLOGY OF HUMAN URINE, 

vestigations : Unclean vessels are often the cause of urine be- 
coming quickly ammoniacal, as in typhoid-fever patients in 
summer. The urine of women, which contains mucus from the 
vagina (in fluor albus) or menstrual blood, readily becomes 
alkaline. The ammoniacal fermentation is caused by a ferment, 
which may be readily obtained artificially on a filter through 
which ammoniacal urine has been passed. If this ferment is 
artificially added to normal urine, it has the power of setting 
up ammoniacal fermentation in it. However, all urines are not 
rendered ammoniacal with equal readiness by the addition of 
the ferment. By prolonged retention in the bladder alone (in 
animals whose urethr?e were artificially closed) the urine is 
not rendered ammoniacal. The mere passing of a catheter im- 
pregnated with the ferment does not always certainly render 
the urine in the bladder ammoniacal. 

2. There is still another cause essentially different from the 
one just described which may render the urine neutral or alka- 
line. This cause lies in the condition of tlie hlood. Under ordi- 
nary circumstances acid urine is secreted from the alkaline hlood. 
The kidneys or their secreting cells must, therefore, have the 
power of separating acid salts from the alkaline blood, or of 
forming them and passing them on into the urine."^ But when 
the blood is excessively alkaline, as a rule, acid urine is no 
longer separated from it, but neutral or alkaline. Thus the 
urine becomes alkaline when a large quantity of caustic alka- 
lies or of carbonates of the alkalies are taken into the system, 
and it continues so until the excess is separated from the blood. 
Caustic soda, lime, potash, and magnesia, and their carbonates, 

*[Dr. Richard Maly (Bericlite der deutschen cliemisclien Gesellschaft, 1876, 
page 164) has partially explained by some diffusion experiments the acidity of 
normal urine. He found that by placing in a diffusion apparatus a mixture of 
the mono-sodic (acid) and di-sodic (allialine) phosphates of sodium, the acid 
phosphate passes through the membrane much more readily than the alkaline, 
so that while the fluid in the dialysor has an alkaline reaction, that without has 
an acid one. This is virtually what takes place in the kidney. The blood con- 
tains both of these phosphates of sodium, the di-sodic phosphate being con- 
stantly deprived of a part of its sodium by uric, hippuric, lactic, and other acids, 
which are produced by the metamorphosis of the nitrogenous tissues. The 
mono-sodic phosphate thus formed then readily diffuses from the blood to the 
urine, and imparts its acid reaction to that fluid, while the principal part of the 
di-sodic phosphate remains in the blood. — Beviser's Note-I 



CHEMICAL REACTION OF THE URINE. 375 

act in this way ; further, all vegetable salts, wliicli are converted 
in the body into carbonates and are eliminated as such in the 
urine (acetates, citrates, malates, and tartrates). All of these 
drugs, when they are taken in large doses as medicines, render 
the urine alkaline, and often in a very short time. Bence Jones 
found that 120 grains of dry tartrate of potassium dissolved 
in four ounces of water made the urine alkaline in thirty-five 
minutes ; two hours later the alkaline reaction had disappeared 
again. Smaller doses, which are not sufficient to render the 
urine alkaline, at least diminish its quantity of acid. 

Food acts in the same way, and according to the nature of 
its constituents sometimes increases the alkalinity of the blood 
and sometimes diminishes it. It is known that the urine of 
carnivorous animals is acid for this reason, and that of herbivo- 
rous animals is alkaline. A similar action of food on the urine 
is shown in man, though usually in a less degree, because his 
diet is in most cases a mixed one. 

But certain processes in the organism also, results of the 
secondary metamorphosis, without doubt exercise an influence 
on the reaction of the urine by changing the alkalinity of the 
blood. The nature of these processes is, however, very obscure 
at present, and it is only by very difficult and complicated in- 
vestigations that we can clear them up. In the meantime the 
following conditions may be designated as probable : 

a. Bence Jones has pointed out that the acid reaction of the 
urine increases and diminishes inversely with the secretion of 
the acid gastric juice. He asserts that the urine is most acid 
at the time when the stomach contains no gastric juice, or when 
this secretion has been returned again to the body ; and that, 
on the other hand, it becomes less acid or even alkaline in pro- 
portion as the acid gastric juice is separated from the blood. 

Unfortunately, the experiments performed by Bence Jones to 
prove this point are not convincing. In these, as in almost all 
of his quantitative examinations of urine, the amount of acid is 
reckoned for 1,000 parts of urine and not for the hourly secre- 
tion, as should be the case if trustworthy conclusions are to be 
drawn from them. Experiments which were performed partly 
by myself and partly by others under my direction invariably 
showed that the greatest quantity of acid passed with the urine 
per hour was in the night, the least was during the hours be- 



376 SEMIOLOGY OF HUMAN UBINE, 

fore noon ; wliile tlie quantity of acid in the afternoon hours 
(after the chief meal) was a mean between the two. These ex- 
periments, therefore, do not agree with the statements of Bence 
Jones, but they do not positively contradict them, since other 
circumstances may influence the amount of acid in the urine. 

Theoretically Bence Jones's hypothesis appears to be very 
plausible : a quantity of acid is separated from the blood with 
the gastric juice, the blood becomes more alkaline, and conse- 
quently the urine secreted at this time contains less acid. It 
is possible, however, that the alkali which was combined with 
the acid of the gastric juice does not remain in the blood, but 
passes over into the bile, so that the alkalinity of the blood 
suffers no change through the secretion of the gastric juice, and 
consequently the secretion of the gastric juice has no influence 
on the acidity of the urine. Kecent investigations of W. Koberts 
have confirmed the statements of B. Jones. (Compare § 127.) 

b. According to the investigations of Liebig and others, the 
muscular juice is acid, or at least it becomes so immediately 
after being expressed. Now since the urine of carnivorous ani- 
mals is rendered acid by the constituents of the meat which 
they take as food, it is probable that in man (and in animals) a 
part of the acid of the urine, perhaps the greatest part, is de- 
rived from the muscular juice produced by metamorphosis and 
passed into the blood, or, in other words, the acid of the urine 
is in part a product of the metamorphosis of the muscular 
tissue. 

That this is the case is indicated by the observation which 
has often been made, that in herbivorous animals which gene- 
rally secrete an alkaline urine, it becomes acid when they starve, 
that is, consume the constituents of their own bodies. 

However, this is not the place to discuss these difficult theo- 
retical questions. From the physician's standpoint the follow- 
ing are the chief points of interest in the reaction of the urine : 

1. The urine has an acid reaction. This is the normal con- 
dition, and has only a negative value for the practitioner, since 
he determines from it the absence of certain diseased condi- 
tions. Further conclusions are obtained in this case, when the 
amount of acid has been accurately determined quantitatively 
(§ 127). A very acid condition of the urine may favor the for- 
mation of certain sediments or concretions, especially uric acid, 



CHEMICAL BEACTION OF THE URINE. 377 

or it may give rise to an irritation of the kidneys and urinary 
passages. 

2. The urine has a neutral or alkaline reaction. This condi- 
tion is always of importance to the physician, and requires an 
accurate investigation. In such a case we must regard the fol- 
lowing particulars : 

a. The alkaline reaction may depend upon carbonate of am- 
monium (red litmus paper becomes blue when dipped in the 
urine, but after drying it becomes red again, and a glass rod 
moistened with hydrochloric acid and held over the urine de- 
velops a white cloud). This always comes (except in the rare 
cases where the carbonate of ammonium is directly eliminated 
with the urine) from the decomposition of urea in the already 
secreted urine ; or, 

b. The alkaline reaction depends upon a fixed alkali, potash, 
soda, or an alkaline earth (red litmus paper is made blue by the 
urine and remains so even after drying, and a glass rod dipped 
in hydrochloric acid and held over it does not show a white 
cloud). The cause in this case may be : 

The medicinal use of caustic or carbonated alkalies, or of 
alkaline salts of the vegetable acids, or a diet rich in the latter, 
or alterations in the metamorphosis, which was briefly referred 
to above. 

The answer to the question as to how far the physician must 
regard a neutral or alkaline condition of the urine, that is, more 
especially in reference to his prognosis and treatment, depends 
chiefly on whether this condition of the urine is temporary or 
permanent. 

If the urine has only a transient neutral or alkaline reaction 
at a certain time of the day, more especially a few hours after 
eating, after certain kinds of food, or on certain days, it has a 
physiological but no practical signification. 

If, however, the urine is frequently or permanently alkaline, 
important semiotic and practical conclusions may be derived 
from it, which are different in different cases : 

1. The cause is a decomposition of the urea within the uri- 
nary passages. The diagnosis of these cases is made from the 
fact that the urine is ammoniacal, and contains mucus and crys- 
tals of ammonio-magnesian phosphate. 

2. If the cause lies in the continued use of caustic alkalies. 



378 SEMIOLOGY OF HUMAN UBIFE. 

their carbonates or vegetable salts, the diagnosis is self-evident 
from the above. 

3. The cause consists in alterations of the metamorphosis. 
These are thus far only imperfectly understood ; but we may 
designate as j)robable : arrest of the muscular metamorphosis, 
weakness of the nervous system, anaemia and chlorosis, defective 
nutrition, and general debility. One of the greatest services of 
Eademacher ^ is that he called attention to the fact that a con- 
stantly alkaline urine is an iron affection, that is, translated 
into scientific language, requires the use of tonic remedies. 
Still, from what has been mentioned above, it is evident that 
this is true only in a limited sense, and, moreover, the pale 
color of the urine in such cases forms a surer indication for the 
careful observer that tonic remedies are indicated than the al- 
kalinity of the urine, which is often absent in such cases. 

The rational treatment of such conditions is frequently very 
difficult. The chief task is always to discover and combat the 
cause of the alkalinity. It is a very bad practice, and the re- 
sult of erroneous chemical reasoning, to give acids in all cases 
in which the urine is alkaline. When the alkaline state of the 
urine depends on an irritation of the urinary passages, which 
is brought about by a too acid and irritating character of the 
urine with the formation of uric acid gravel, on the contrary, 
in addition to demulcent remedies, alkaline carbonates or ace- 
tate of potassium are the best remedies. 

The assertion, which has often been repeated, that benzoic 
acid taken internally renders alkaline urine more quickly and 
certainly acid than other acids, has not been confirmed by the 
results of numerous experiments performed by me with refer- 
ence to this point. 

III. THE APPEARANCE OF UNUSUAL (ABNORMAL) CONSTITUENTS 

IN THE URINE. 

All changes of the urine which come under this head have a 
great practical importance, for in all cases we must infer the 
existence of diseased conditions. Every abnormal constituent 
which appears in the urine has its own signification ; we shall, 

* Reclitfertigung der verstandesrechten Erfahrungslieillehre, 3. Aufl,, Bd. 2, 
S. 211, et seq. 



TIJSfUSUAL CONSTITUENTS IN THE URINE. 379 

therefore, immediately proceed to consider the various abnor- 
mal constituents. 

§ 97. Albumen. 

A. The detection of albumen in urine has already been described 
in § 23. But since it is not always very easy, and certain pre- 
cautions are required, and, moreover, physicians may very easily 
be led into error in testing for this substance by sometimes 
overlooking albumen when present, and sometimes wrongly 
considering it to be present when this is not the case, it ap- 
pears best to return to the subject once more. 

We detect albumen in the urine : 

1. By adding nitric acid. When much albumen is present, an 
intense white turbidity is formed in it, or the fluid changes to 
a white pulp. In such cases no doubt can exist about the 
presence of albumen in the urine after this reaction. But the 
case is different when only a small quantity of albumen is 
present ; the slight cloudiness which occurs may then be over- 
looked, or a cloudiness produced by the presence of other mat- 
ters, such as urates, mucus, and the like, may be considered as 
due to albumen. It is best, therefore, to proceed with a cer- 
tain caution in adding nitric acid. 

As Heller has advised, a somewhat broad liquor glass is the 
best vessel to use in performing this test ; it is two-thirds filled 
with urine, and a little nitric acid is allowed to flow down the 
side of the glass slowly and carefully, so that it may collect at 
the bottom. If albumen is present, a turbid zone sharply de- 
fined on the upper and lower surface is formed above the acid, 
which is not readily overlooked on account of the contrast; 
this process, therefore, may serve to detect the slightest traces 
of albumen in the urine. A cloudiness of the urine, depending 
on the presence of urates, may be produced by the nitric acid, 
but this cloudiness, when the test is performed as above, is 
sharply defined only on the lower surface toward the layer of 
acid, while above it pervades almost the whole urine in the 
form of cloudy streaks. An experienced person is able by this 
procedure to distinguish between the zones of albumen and 
urates when they occur together. It is observed that imme- 
diately above the clear layer of acid there is a cloudy zone of 
coagulated albumen sharply defined both on the upper and 



380 SEMIOLOGY OF HUMAN' URmE. 

lower surface ; above this there is a zone of clear urine, and then 
a layer which is made cloudy by urates.^ (Compare also § 23, 
page 95, et seq.) 

2. By boiling the urine, so that the albumen is coagulated, 
and, when much albumen is present, a flocculent coagulation is 
the result ; when little is present there is a cloudiness only. 

But this test may deceive us also ; a cloudiness of the urine 
may result from boiling when no albumen is present. This 
cloudiness in the majority of cases is caused by the earthy 
phosphates ; in very rare cases (in osteomalacia) it depends on 
the presence of a peculiar protein substance different from 
albumen.t Both these last-named turbidities are very readily 
distinguishable from that due to the albumen, since they dis- 
appear again after the addition of a little acid (acetic or hydro- 
chloric acid), which is not the case with the cloudiness due 
to albumen. These two turbidities may, furthermore, be dis- 
tinguished from each other by the fact that the protein sub- 
stance is dissolved by caustic potash, but the earthy phos- 
phates are not. The protein substance is also distinguished 
from albumen by the fact that it is not precipitated by nitric 
acid. 

Albumen in urine, moreover, is not under all circumstances 
coagulated by boiling ; for instance, not when the urine is al- 
kaline. We must, therefore, always test the reaction of the 
urine before boiling, and, if it is alkaline, we must carefully 
neutralize it with acetic or nitric acid. 

Sometimes, though very rarely, albumen is not precipitated 
even in an acid urine by boiling. This is the case when the 
urine contains a large quantity of free hydrochloric or nitric 
acid, each of which may form a compound with albumen ^thich 
is soluble in both cold and boiling water. (Bence Jones.) 

When the physician wishes to decide the question with cer- 
tainty, whether a specimen of urine contains albumen or not, it 
is best to try both the nitric acid and the heat tests. 

These reactions, hoAvever, only allow of the detection of that 
form of albumen which occurs most frequently in the urine, and 
which especially forms so-called albuminuria (serum albu- 
men). Besides this, still other varieties of albumen may occur 

* Heller's ArcMv ftir Chemie und Microsc, 1852, p. 163, et seq. 
f Heller in his Archiv, 1853, p. 167. 



VNU8UAL CONSTITUENTS IN THE URINE. 381 

in tlie urine, all of which are not indicated by these reactions, 
but require special chemical tests for their detection and separa- 
tion. For particulars on this point see below (II.). 

B. What significance has the presence of albumen in the 
urine for the physician ? 

The answer to this question, which has occupied pathologists 
and physicians, is very difficult, and if we do not proceed very 
carefully, we run the risk of drawing false conclusions when 
the urine contains albumen, as has very frequently happened 
to physicians, many of whom are inclined to regard every albu- 
minuria as indicative of a dangerous organic disease of the kid- 
ney (morbus Brightii in its broadest sense). The following 
points will assist us in considering the diagnosis and prognosis : 

1. The albumen in the urine may depend on an organic dis- 
ease of the parenchyma of the kidney, which is combined with 
its serious change and disorganization (exudation into the renal 
tubuli, alteration and separation of the epithelium — Bright's 
disease in the broadest sense ; amyloid degeneration of the re- 
nal capillaries, etc.). This supposition becomes almost a cer- 
tainty when casts are found in the urine at the same time, less 
of a certainty when only separated epithelial cells from the 
urinary tubules are found. (Compare § 116.) It is rendered 
probable by the simultaneous presence of dropsy, or when a 
a large amount of albumen has been present in the urine for a 
long time, weeks or months. The prognosis in such a case is 
usually unfavorable. Still, a few apparently very bad cases 
running an acute course may completely recover, and chronic 
cases may last very long (for years) without seriously endanger- 
ing the health or life. 

2. The albumen In the urine may depend on a local disease 
of the uropoetic system when Bright's disease does not exist. 

When blood, blood plasma, or pus is mixed with the urine it 
contains albumen. In this case, however, the urine also con- 
tains, besides albumen, blood corpuscles, blood coloring matter, 
fluid or coagulated fibrine, and pus corpuscles. The diagnosis 
of these foreign constituents and their signification may be 
found in the following sections. 

In rare cases the urine may also contain albumen from an 
abundant mixture with the spermatic fluid.* 

* Bence Jones, Animal Chemistry, 1850, p. 108. 



382 SEMIOLOGY OF HUMAN URINE. 

But tlie urine may also contain albumen without tliis admix- 
ture from an irritation and liypersemia of the kidneys, namely, 
passive hypersemia, in which the capillaries of the kidney ap- 
pear to be so modified that they allow a little albumen to filter 
through their walls into the urine. This is sometimes observed 
after the use of powerful diuretics, cantharides, etc., after liga- 
ture of the renal veins or of the aorta below the origin of the 
renal arteries, after the injection of a large quantity of water 
into the blood, and especially under conditions which increase 
the blood pressure in the renal vessels. Many diseases, with- 
out doubt, may have a similar action on the kidneys, and there- 
by render the urine albuminous. 

3. But probably albumen may pass into the urine also on 
account of certain alterations in metamorphosis and especially 
in the blood, without local disease of the kidneys. But we 
know very little as yet of these relations and their mode of 
action ; however, the following points may be laid down with 
more or less probability : 

a. In that condition of the blood in which the serum be- 
comes poor in albumen and rich in water (hypalbuminose, 
hydraemia) we sometimes see albumen appear in the urine. 

b. When albumen in solution is injected into the blood of 
animals, or when they are largely fed with albumen, we some- 
times find the urine albuminous, sometimes not. A further 
pursuit of these experiments by Corvisart, Schiff, Stockvis, 
Parkes, Pavy, and others has led to the opinion that certain 
forms of albumen pass through the walls of the renal vessels 
more readily than others, and it has been supposed, further, 
that certain modifications of the blood albumen, which are 
formed in disease by abnormal metamorphosis, may give rise 
to albuminous urine. 

The experiments of Pavy * indicate this. They show that the 
albumen contained in the urine does not always act in the same 
way on dialysis, and, moreover, it has difi'erent qualities from 
the albumen of the blood serum. Terrell t declares that in 
temporary albuminuria and in the beginning of Bright's dis- 
ease the albumen in the urine possesses different characteristics 



* Lancet, May, 1868. 

f Gaz. des Hopit., 1863, 63. 



UJS'USUAL CONSTITUENTS IN THE URINE. 383 

from that in an advanced case of Briglit's disease. In the first 
case, from the presence of paralbumen a precipitate produced 
by strong alcohol is dissolved again by a large amount of water, 
and potassio-cupric tartrate causes, especially when heated, a 
beautiful violet color. In a marked case of Bright's disease, 
on the contrary, the alcoholic precipitate is not dissolved again 
by water and the copper solution produces no violet color. 
Others (Gerhardt, Masing, Schultzen and Eiess, Edlefsen) 
have found varieties of albumen in the urine of patients which 
differed from ordinary serum albumen: paralbumen, paraglo- 
bulin, peptone, etc. (Compare below, page 384, et seq). 

A. Creitte * has also communicated experiments on the action 
of serum albumen when injected into the blood. He found that, 
as a rule, an albuminuria was produced by it which was only 
transitory, but sometimes was accompanied by very bad results. 

Whether in the cases of the separation of albumen considered 
under a and b, a visible alteration in the kidneys (hypersemia 
and dilatation of the vessels, partial separation of the epithe- 
lium of the urinary tubules) precedes or not, cannot usually be 
determined. But this much is certain, that this affection of the 
kidney when it exists is only temporary ; and consequently from 
the presence of albuminuria alone we cannot conclude that 
there is material alteration of the kidneys (so-called Bright's 
disease), but only when at the same time there are other signs, 
such as the presence of renal casts in the urine. It is self-evi- 
dent, moreover, that we should only think of Bright's disease 
in those cases in which the urine has been constantly and for 
some length of time albuminous. 

If we have reason to believe that Bright's disease does not 
exist, it remains to determine whether the albuminuria is de- 
pendent on an inflammation of the kidneys or on a change in the 
blood. The answer to this question naturally requires a further 
examination of the case, and is sometimes positive, but often 
only conjectural It is usually of great value in reference to 
the prognosis and treatment, especially when it is a question 
whether we shall use diuretics or not. 

The following suggestions may serve as hints in forming an 
opinion concerning many cases of albuminuria : 

* Henle und Pfeuffer's Zeitsclir, 36, p. 90, et seq. 



384 SEMIOLOGY OF HUMAN UHIJYE. 

"Waldenstrom repeatedly observed the occurrence of albumen 
in tlie urine after the external or internal use of carbolic acid. 

Hegar and Kaltenbach ^' frequently, but not always, found the 
urine to be albuminous after the administration of chloroform. 

E. Gerhardtt repeatedly observed that patients who fre- 
quently or constantly had a temperature of over 40° C. had albu- 
men in their urine, if not in the ordinary form, at least in a form 
described by him as latent, which is not precipitated by boiling 
or on the addition of nitric acid, but is precipitated by alcohol 
(peptone). 

H. Senator X shoived that several different albuminoid bodies 
occur in the urine, yet in different amounts under different con- 
ditions and in varying proportions to each other. Indeed albu- 
minoid bodies occur in the urine which were not previously 
found in the blood, and, conversely, some are absent from the 
urine which are found in the blood. The albuminoid bodies 
of which we speak are : 

1. Globulin or j^ccy^f globulin ; it is detected by diluting the albu- 
binous urine with water until its sp. gr. is 1'002 or 1'003, and 
conducting carbonic acid gas into it for two or four hours. The 
cloudiness which is thus produced forms usually, but not always, 
after one or two days, a milky precipitate, w^hich dissolves again 
on adding very dilute hydrochloric acid or a solution of chloride 
of sodium and concentrated acetic acid. Cases of amyloid de- 
generation of the kidney showed the greatest amount of para- 
globulin, and cases of acute nephritis contained a large amount 
of it. On the other hand, very little or no paraglobulin was 
found in chronic diffuse nephritis. In catarrh of the bladder 
the urine always contained paraglobulin, besides a relatively 
scanty amount of albumen. 

2. Alkali albuminate, that is, a body which is obtained from 
blood serum after precipitating the paraglobulin with acetic 
acid, either does not appear in the urine at all, or only in very 
slight traces. 

3. Peptone (precipitable with alcohol after separating the 
other varieties of albumen by boiling) is contained in small 

* Vircliow's Archiv, 49, p. 437, ct seq. 
f Deutsclies ArcMv f. klin. Med., 1868, v., p. 212, et seq. 

\ Ueber die im Harne vorkommenden Eiweisskorper, etc. , in Vircliow's 
ArcMv, 1874, Band GO, p. 476, ct seq. 



UNUSUAL CONSTITUENTS IN TEE URINE. 385 

amount in every albuminous urine, and, according to Gerliardt 
(see above), under certain circumstances occurs in urine which 
contains no albumen coagulable by heat. 

Sometimes a quantitative estimation of the albumen separated 
by the urine is desirable, especially in cases where we wish to 
know how much is thus removed from the body, and whether 
an essential impoverishment of the blood is to be feared from 
this cause or not. (Hypalbuminosis, hydraemia). 

In order to make such quantitative estimations of the albu- 
men practically serviceable to the physician, we mention the 
following considerations, and we must not only determine the 
percentage of albumen in the urine, but must also calculate it 
for a given time, preferably twenty-four hours. 

The quantity of albumen which is passed with the urine in 
albuminuria varies greatly from a minimum (less than one grm. 
daily) to 20 and even 30 grm. of dry albumen in twenty-four 
hours. Keeping these facts in mind, the loss of albumen with 
the urine may be considered in the following categories : 

It is hisignificant and has hardly any influence on the compo- 
sition of the blood and metamorphosis, when the amount sepa- 
rated is less than 2 grm. in twenty-four hours. 

The loss is moderate when the daily quantity averages 6 or 8 
grm. 

The loss is considerahle when it exceeds 10 or 12 grm. 

20 grm. and more of albumen in twenty-four hours is an un- 
usually large quantity and belongs among the exceptions ; it 
rarely lasts long at this height. 28 '3 grm. of albumen was the 
maximum quantity which I have thus far seen pass off with the 
urine in twenty- four hours in a large number of observations. 

If we seek to obtain an approximate idea as to the action of 
such a loss of albumen on the quality of the blood, and espe- 
cially whether it can bring about a morbid diminution of the 
albumen in the blood serum (hypalbuminosis, hydraemia), we 
must proceed as follows : We will assume the most unfavorable 
conditions, in which the serum constitutes only about one-half 
of the whole amount of blood, and according to which an adult 
possesses about 6,000 grm. of blood serum containing 8 per cent., 
in all only about 480 grm. of albumen. Moreover, if we sup- 
pose that as long as the albuminuria lasts, no albumen is formed 
from the protein bodies which are taken as food, and also, as 
25 



386 SEMIOLOGY OF HUMAN URINE. 

is scarcely probable, none from the lisematoglobulin of the 
broken-up blood corpuscles. If now 10 grm. of albumen are 
passed daily on an average, in ten days 100 grm., the amount 
of albumen of the blood serum sinks to 380 grm., and the 
relative amount in the blood serum is diminished from 80 to 
64 parts in a thousand, which corresponds to a tolerable de- 
gree of hydraemia. Aftar twenty-six days such an albuminu- 
ria would have diminished the amount in the blood serum to 
37 parts in the thousand — a number which nearly corresponds 
with the minimum amount of albumen in the blood serum in 
hydrsemia observed by Becquerel and Rodier. These consid- 
erations show how, under the above conditions, a high degree 
of hydraemia may be produced in a relatively short time by an 
abundant albuminuria. Experience teaches us, however, that 
the action of an albuminuria on the quality of the blood is 
only rarely so considerable, except in a few very acute cases 
accompanied by fever, and in patients whose appetite and di- 
gestion are lost. When we remember that 100 parts of meat 
contain about 15 or 20 parts of protein substances, which, if 
the digestion is good, are almost wholly converted into a solu- 
ble form of albumen, and pass into the blood, under favorable 
circumstances a loss of 10 grm. of albumen daily may be re- 
placed by the additional ingestion of about three ounces of meat 
or a corresponding quantity of other food containing protein ; 
and, in fact, I have often seen in patients with a fair digestion 
and without fever, who were well nourished, a moderate degree 
of albuminuria last for months or even years without causing a 
perceptible hydrsemia or symptoms which pointed toward it. 

The methods which are used to determine the albumen in 
the urine quantitatively were described in § 75. 

A. Stscherlakoff and Chomjakoff - have undertaken compara- 
tive examinations as to the accuracy of these different methods. 
According to these authors the estimation of albumen by coagu- 
lation and weighing (compare page 293, et seq.) does not give 
perfectly accurate results, because all of the albumen is not pre- 
cipitated by it. "When the urine contains 0'5 per cent, of albu- 
men, from four to eight times as much albumen remains dis- 
solved as is precipitated. "When it contains 1 per cent., that 

* Deutsclies Arcliiv f. klin. Med., 1870, viii., p. 218, et seq. 



UNUSUAL CONSTITUENTS IN THE URINE, 387 

wliicli remains dissolved nearly equals tliat wliicli is precipi- 
tated. When tliere is more than 2 per cent, of albumen, about 
one-third of it remains in solution. 

The estimation of albumen from the difference of the sp. gr. 
before and after coagulation of the albumen by the method 
of Lang and others (compare page 297, 3) gives very inaccu- 
rate results. 

On the other hand, the optical determination of the albumen 
by the polariscope (compare page 296, B) is the most accurate, 
and at the same time the simplest and quickest method, 

P. Liborius ^ has also undertaken comparative experiments 
as to the accuracy of the different methods of determining albu- 
men. According to him its precipitation by alcohol, by which 
peptone is also obtained, gives the most accurate results known 
at present. 

For mere approximate determinations of the amount of albu- 
men in the urine, when the physician only wishes to know 
whether the separation of albumen in albuminuria is inconsid- 
erable or large, and especially whether it increases or dimin- 
ishes, the following procedure, which does not require extensive 
apparatus, may be adopted : 

Test tubes of the same diameter are to be chosen in precipi- 
tating the albumen from the urine by boiling or adding nitric 
acid, and the precipitate of albumen is allowed to remain at rest 
for twelve or fourteen hours. The relative amount in compari- 
son with the quantity of urine used in the experiment may thus 
be easily approximately estimated. If the tests of the urine of 
different days are preserved, their amounts of albumen may be 
compared, and we may easily see whether it increases or not. 
This estimation is more exact, when we use, instead of test tubes 
which are rounded at the bottom, not too narrow glass tubes 
with a diameter of from J to J of an inch and an even bore, 
which are closed below by a tightly fitting cork cut off squarely, 
and into which the boiled urine is poured. If the albumen 
precipitate has completely settled in these after twelve or 
twenty-four hours, we can estimate with the aid of a measure 
held near the tube how many tenths or hundredths of the whole 

^Beitrage zur quantit. Eiweissbestimmung im Deutscli. Arcliiv f. klin. 
Med X., 1872, p. 319, et seq. 



388 SEMIOLOGY OF HUMAN URINE. 

quantity of urine tlie precipitate of albumen occupies. But we 
must not forget that only the relative and not the absolute quanti- 
ty of albumen contained in the urine is learned in this way. 
Apart from this also such calculations always remain somewhat 
uncertain ; for according as the albumen coagulates on boiling 
in coarser or finer particles, and according to the specific gravity 
of the urine which remains behind, the precipitated albumen 
sometimes assumes a larger and sometimes a smaller volume, 
and experiments, in which the albumen has been determined at 
the same time by weight and by volume, have shown me that 
in estimating it according to the latter method errors of 30 
and even 50 per cent, may be made. Therefore the statements 
of some of the French pathologists with reference to the separa- 
tion of albumen in albuminuria under th3 influence of various 
agencies, as far as they are founded on the estimation of the 
albumen by volume, must be received with great caution. 

§ 98. FlBEINE. 

Fibrine under various circumstances may appear in the urine 
sometimes coagulated and sometimes in solution. 

Coagulated fibrine appears either in large particles visible to 
the naked eye, as blood coagula, Avhich cannot be mistaken (see 
the following section), or, more rarely, in the form of colorless, 
sometimes solid, sometimes gelatinous fibrinous coagula; or 
again in very small particles visible only with the microscope in 
the form of so-called urinary casts or cylinders. (See Urinary 
Sediments, § 116.) 

Dissolved fibrine in the urine forms the so-called coagulable 
urine, which is characterized by the formation of fibrinous 
coagula in it after some time (generally several hours after it 
has been passed); sometimes these only cover the bottom of 
the vessel and form a sort of coherent sediment in the lower 
part of the urine; sometimes it occupies the whole mass of 
urine and transforms it into a completely gelatinous mass. This 
coagulable urine is seen in this country very rarely, but outside 
of Europe it is met with more frequently (Brazil, Isle de France, 
etc.). 

The fibro-gelatinous mass which forms may very readily be 
confounded with that which occurs much more frequently with 



UWUSUAL CONSTITUENTS IN THE UTJNE, 389 

lis, and wliicli is formed by tlie action of carbonate of ammo- 
nium upon the pus corpuscles contained in the urine, as often 
happens in catarrh of the bladder. (Compare § 113 and § 114) 

Coagulable urine sometimes contains blood also. In such 
cases we cannot be sure that the urine contains fibrine as well 
as blood, unless the fibrinous coagulum is so large that it can- 
not be ascribed to the presence of the blood alone. 

I saw such a case in a woman who was suffering from Bright' s 
disease. Here, for a long time, a very pale-red fibrinous coagu- 
lum containing numerous pus corpuscles and a few blood cor- 
puscles was regularly formed at the bottom of the glass some 
hours after the urine was passed. The blood corpuscles, how- 
ever, were far too few to indicate that the blood which they 
represented could have yielded the whole of the fibrinous co- 
agulum. 

Impoy^tance. Fibrine in the urine, whether dissolved or co- 
agulated, always indicates that at some part of the uropoetic 
system an exudation of a fibrinous fluid (blood plasma) has oc- 
curred. In most cases this fibrine comes from the kidneys, but 
it may arise from some other part of the urinary passages. 



§ 99. Blood in the Urine. 

(Blood Corpuscles. Blood Coagula.) 

A. Detection, The urine has the color of blood, and under 
the microscope shows the characteristic blood corpuscles. (See 
§ 51.) If the quantity of blood is very small, we cannot be sure 
of finding the blood corpuscles, unless the urine has stood a 
long time. They then become deposited as a red sediment on 
the bottom. In this way we may recognize even a very small 
amount of blood with the unaided eye : should any doubt exist 
as to the nature of the sediment, it must be cleared up by a 
microscopic examination. 

The blood may coagulate, if the quantity is rather large, 
either within the urinary tract, when the large blood coagula 
may stop up the urinary passages, causing dysuria, strangury, 
or retention of the urine, sometimes giving rise to the formation 
of urinary calculi even, or the coagulation of the blood may 
take place in the urine after it has been passed. (Compare § 98.) 



390 SEMIOLOGY OF HUMAN UBmE. 

B. Importance. Blood corpuscles or blood coagula in the 
urine always indicate that a haemorrhage has occurred some- 
where in the urinary passages. The causes of such a haemor- 
rhage and its results are very various, and this is not the place 
to describe at length all of the possible causes which may give 
rise to it. The following considerations will serve as guides in 
the examination : 

When the urine contains very much blood, it usually comes 
from the pelvis of the kidney, the ureters, or the bladder, rarely 
from the kidneys themselves. Sometimes the cause of the 
haemorrhage depends on a general scorbutic condition, the 
diagnosis of which presents no difficulties to the careful physi- 
cian. 

With this exception haemorrhages from the pelvis of the 
kidney and the ureters is most frequently caused by renal 
calculi, more rarely by ulceration of these parts from other 
causes. In such cases, in addition to the haemorrhage there 
usually exists an inflammation of the pelvis of the kidney and 
of the ureters (pyelitis) ; the urine contains, in addition to the 
blood, pus corpuscles also, sometimes fragments of calculi or 
gravel ; there is pain in the region of the kidneys and in the 
course of the ureters. This set of symptoms usually establishes 
the diagnosis. 

If pain is wanting in the region of the kidneys or in the 
course of the ureters, the source of the haemorrhage is proba- 
bly to be found in the bladder. The causes may be : hyperae- 
mia (so-called vesical haemorrhoids), vesical calculi, erosions, 
and ulcerations of the mucous membrane of the bladder, or 
serious organic lesions of the bladder, especially cancer, which 
has become softened. The other symptoms of disease of the 
bladder which are present in addition to the bloody urine in 
such cases, generally enable us to readily discover the source 
of the haemorrhage, and a careful examination and continued 
observation, as a rule, will give us a clue to the nature of the 
disease. 

Sudden or temporary symptoms of disease of the bladder 
(dysuria, ischuria) occurring without premonitory symptoms 
may arise when the haemorrhage has taken place, not in the 
bladder, but in the pelvis of the kidneys or in the ureters. 
This happens when the blood which has found its way to the 



UNU8UAL CONSTITUENTS IN THE URINE. 391 

bladder coagulates there, and tlius occludes tlie urethral ori- 
fice, or when blood coagula are washed out of the ureters into 
the bladder and in the same way render micturition difficult 
or impossible. 

If the quantity of blood in the urine is small, and there are 
symptoms present which indicate disease of the urinary pas- 
sages, it is probable that the blood has come from the paren- 
chyma of the kidneys, and especially from the vessels of the 
Malpighian corpuscles, and we have to deal with a disease 
which belongs under the large class of so-called Bright' s dis- 
ease. In such cases when the haemorrhage is not very transi- 
tory, the urine usually contains besides blood, fibrinous casts, 
or pus corpuscles and granule cells, whose presence not only 
strengthens the diagnosis, but also sometimes enables us to 
diagnosticate with more or less probability a certain form of 
kidney disease. 

In all cases of haemorrhage in the uropoetic system the physi- 
cian must not be contented with simply diagnosticating the seat 
and cause of it, but must also try to determine the possible 
consequences for the purposes of prognosis. 

The following considerations may be of service in this re- 
spect : 

A haemorrhage from the urinary passages is only rarely so 
considerable that it directly causes an essential diminution of 
the blood corpuscles in the body, and thereby brings about 
anaemia or oligocythsemia. 

More frequently the evil consequences arise as follows : The 
effused blood coagulates wholly or partially in the urinary 
passages and occludes the ureters or urethra, and thus hinders 
the evacuation of urine, or these coagula may give rise to the 
formation of permanent concretions (urinary calculi) in the 
urinary passages. Even in those cases in which the quantity 
of effused blood is very slight, small coagula may become the 
nuclei of future urinary calculi. 

In forming the prognosis of a haemorrhage, in addition to 
these possible results we must always take into account the re- 
sults of the process which gave rise to the haemorrhage : the 
affection of the kidney, the pyelitis, the disease of the bladder, 
etc. 

Every specimen of urine which contains blood corpuscles 



392 SEMIOLOGY OF HUMAN UEIJVE. 

must also contain fibrine and albumen, because these substances 
form integral constituents of the blood. Only a careful inves- 
tigation based on approximate quantitative determinations of 
these three constituents of the blood can decide whether the 
whole quantity present in the urine is derived from the blood 
which has been effused, or whether in addition to the blood 
there has been an exudation of fibrine or of albumen. (Compare 
§98.) 

§ 100. Dissolved Blood. Dissolved H^matoglobulin. 

(Haemoglobin and Metliaemoglobin.) 

Sometimes the urine has a bloody color or is reddish brown, 
brownish black or even inky black, and yet no blood corpuscles 
can be detected in it by the most careful microscopic examina- 
tion. If, however, such urine be boiled either alone or after 
the careful addition of a little acetic acid, a more or less abun- 
dant brownish-red coagulum forms in it, which is precisely 
similar to that which blood diluted with water gives on being 
boiled. If this coagulum is then boiled with alcohol which 
contains sulphuric acid, the fluid becomes colored reddish 
brown by dissolving haemoglobin. We can thus, especially 
when the spectral analysis is employed, prove with certainty 
the presence of dissolved blood pigment in the urine, and at 
the same time discover whether it consists of original haemo- 
globin, of altered haemoglobin (methsemoglobin), or of hsematin. 
(See § 51.) 

Such urine is occasionally met with in diseases which are 
associated with what is called a dissolved state of the blood, 
as in scurvy, in putrid and typhus fevers, in malignant remit- 
tent fever, and after the inhalation of arseniuretted hydrogen 



Examples. A., a young man, suffering from a severe attack 
of typhoid fever, passed at the height of the disease, for several 
consecutive days, urine of a blood-red color, which under the 
microscope showed no traces of blood corpuscles, but on boil- 
ing gave an abundant coagulum of haemoglobin. After a few 

^ J. Vogel im Archiv d. Vereins f . gemeinscli. Arbeiten., Band 1, Heft 2, p. 



UNUSUAL CONSTITUENTS IN THE URINE. 393 

days this state of the urine disappeared, and the patient re- 
covered slowly though perfectly. 

X., in perfect health, while performing an experiment, inhaled 
a gaseous mixture, which besides atmospheric air contained 
hydrogen mixed with some arseniuretted hydrogen. He be- 
came momentarily ill, but soon recovered. The urine which he 
passed a short time afterward was inky black ; it contained no 
blood corpuscles, but on boiling yielded an abundant coagulum 
of haemoglobin. This condition of the urine lasted about twenty- 
four hours. 

Also, some smelters, who inhaled arseniuretted hydrogen in 
the extraction of silver from the ore and suffered from poison- 
ing in consequence, three of the nine cases affected proving 
fatal, passed bloody urine.* 

A dog which was allowed to inhale a large quantity of arseni- 
uretted hydrogen experimentally, also passed a urine of a dark 
blackish-brown color containing a large amount of hgemoglobin. 

Eecently, since the operation of transfusion has been per- 
formed repeatedly, a number of the patients operated upon 
have also passed dissolved blood-coloring matter with the 
urine, t 

The passage of haemoglobin with the urine in such cases 
may perhaps be explained in the following way : The blood 
corpuscles are being constantly decomposed in the body by the 
metamorphosis of tissue, and haemoglobin is thereby set free. 
When the metamorphosis takes place normally, it is probable 
that this haemoglobin which is set free, always only in very 
small quantity, is further decomposed : the globulin is finally 
removed from the body in the form of urea and uric acid ; the 
haematin also undergoes further change, and is probably sepa- 
rated fron the body finally as urinary and biliary coloring mat- 
ter, so that in the normal course of metamorphosis, haemoglo- 
bin never appears in the urine. When, however, in patholo- 
gical processes very large quantities of blood corpuscles are at 
once decomposed, the amount of haemoglobin present in the 

* Trost in Eulenberg's Vierteljahrssclir. f. gericlitliche Medicin u. offentl. 
Sanitatswesen, Band 16, p. 269, et seq. 

f Oehme, Sitzungsbericht d. Dresdner Gesellscli. f. Natur. dun Heilknnde v. 
11. April, 1874. See also Landois, Centralbl. f. d. medic. Wissenscli., 1873, No. 
56 and 57. 



394 SEMIOLOGY OF HUMAN URINE. 

blood is so great tliat the wliole of it cannot undergo the nor- 
mal change, and a part of it then apparently passes unchanged 
into the urine, just as happens with other matters which do not 
usually appear in the urine, as, for example, sugar, biliary sub- 
stances, and perhaps also albumen when present in the blood 
in excess. 

This is apparently confirmed by the experiments of Ponfick,"^^ 
which showed that small quantities of haemoglobin introduced 
into the vascular system of animals are decomposed by meta- 
morphosis and disappear, while large quantities give rise to 
liEemoglobinuria and are in part separated unchanged by the 
kidneys. 

Importance. The presence of haemoglobin in the urine is 
important to the physician in two ways. 

1. It indicates that there has been an excessive pathological 
decomposition of blood corpuscles. Under this head there are 
two sorts of cases which we must distinguish in practice : 

a. The cause of the decomposition of the blood may be a 
temporary one, in which case the evil results are confined to the 
loss of a greater or less quantity of blood corpuscles ; the prog- 
nosis is favorable, as in the examples given above. 

b. The cause of the decomposition of the blood may operate 
permanently ; a peculiar dissolution of the blood is thereby 
brought about which endangers life. The prognosis is unfavor- 
able or at all events doubtful. It is seen in cases of severe 
scurvy, in typhus with dissolution of the blood, in septic fevers, 
etc. 

2. We know from the observations of Meckel, Heschl, Fre- 
richs, and particularly from the beautiful experiments of Jul. 
Planer,t that in certain cases, and very probably in those cases 
in which a large amount of haemoglobin is set free, granular 
pigment collects in the blood and may produce serious results 
by obstructing the capillary blood vessels, especially in the 
brain (melanaemia). It, therefore, appears advisable to exam- 
ine the blood microscopically in such cases for any deposits of 
pigment which may occur before giving the prognosis. In such 

* Vircliow's Arcliiv, Band 62, p. 328, ct seq. 

\ Ueber das Vorkommen von Pigment im Blute, Zeitsclir. der Wiener Aerzte, 
1854, p. 127 and 280. See also : Oppolzer, Wiener med. WocTienschr. , 1860, 25 
and 26 ; Mettenlieimer, Wiirzburger med. Zeitsclir., 1862, p. 1, et seq. 



UNUSUAL CONSTITUENTS IN TEE URINE. 395 

cases of melanaemia collections of pigment sometimes occur in 
the urine. (See § 116, p. 437.) 

§ 101. Fat.* 

Our knowledge concerning tlie occurrence and signification 
of fat in the urine is still very incomplete. We do not know 
with certainty how often, in what quantity, and under what 
conditions it appears in normal urine : and the little which has 
hitherto been ascertained of its occurrence in pathological cases 
also appears unsatisfactory. The subject, therefore, requires 
further investigation ; however, what is already known indi- 
cates that the occurrence of fat in the urine promises to be of 
importance in the recognition and prognosis of many patholo- 
gical conditions, especially of fatty degeneration of the kidneys. 

A. Detection. To ascertain the presence of fat in the urine 
we resort to the process given in § 33. It is best to proceed as 
follows : 

1. Sometimes we are able with the unaided eye to see fat 
drops in the urine similar to those which are seen floating on 
soup. These must be further tested by the very simple expe- 
dient of ascertaining whether the greasy spots which they make 
on paper remain after the paper has been dried. In all such 
cases, however, the physician must first assure himself that the 
fat in the urine is not accidental before he admits its existence 
— that it has not become mixed with the urine from unclean 
oily or fatty urine glasses, chamber vessels, medicine glasses, 
etc. This is a source of error which is far from uncommon. 

2. In other cases the fat is recognized by the microscope. 
It appears in the form of drops or granules familiar to all mi- 
croscopic observers, either free or enclosed in cells, masses of 
exudation, fibrinous casts, etc. To find them w^e must either 
seek on the surface of the urine, where free fat drops usually 
float on account of their light specific gravity, or at the bottom 
of the urine when the fat is enclosed in cells or coagula which 
form sediments. 

" C. Mettenlieimer, Arcliiv f. gemeinsch. Arbeiten, Band 1, Heft 3, p. 374. 
A. G. Lanz, De Adipe in Urina, Dorpati, 1851. L. Beale, London Microsc. 
Journ., January, 1853, 1, 2. Sclimidt's Jahrbuch., 1873, 7, p. 7. Kletzinsky, in 
Heller's Arcliiv, 1852, p. 287. 



396 SEMIOLOGY OF HUMAN UBINE. 

3. But the fat may be in such a minute state of division in 
the urine that it cannot be recognized even with the microscope. 
Then there is nothing left but to test the fat chemically as de- 
scribed in § 33, C, and § 82. 

B. Importance. As far as we can judge at present, fat in the 
urine, when not of mere transitory occurrence, and when it lasts 
a considerable time, is of importance to the physician chiefly 
from the fact that its presence leads to the suspicion of a fatty 
degeneration of the kidneys, which may exist alone (fatty kid- 
ney), or may be associated with contraction of the organ, as in 
one of the various forms of so-called Bright's disease. In the 
last case the formation of fat occurs either in the secreting cells 
of the kidney (epithelium of the urinary tubules), or it arises 
from the fatty metamorphosis of exudations deposited in the 
kidneys. 

It is not improbable, however, that fat in the urine may de- 
pend on other causes besides those mentioned here : 

Upon a fatty degeneration of the epithelial cells of the ure- 
ters and the bladder. 

Upon an excessive amount of fat in the blood, which might 
possibly occasion the passage of fat into the urine without a 
coexistent fatty degeneration of the parenchyma of the kidney. 

Thus Bernard sometimes, though not always, saw fat appear 
in the urine of dogs who were fed on a very fatty diet. 

For a more accurate study of these relations it will usually 
be necessary to determine the amount of fat in the urine quan- 
titatively^ either by an approximate estimation or, more accu- 
rately, by chemically extracting and weighing the fat which is 
passed in a given time — say twenty-four hours. Such a quan- 
titative determination of the fat should be carried out accord- 
ing to § 82, or better still by Kletzinsky's method. He first 
boils the evaporated urine with alcohol, to which a couple 
of drops of acetic acid have been added, then evaporates to 
dryness again on the water bath and afterward extracts with 
ether. By this process the organic matter is better prepared 
for the subsequent removal of the fat by ether, and any saponi- 
fied fat which may be present is deprived of its alkaline base 
and incorporated with the ethereal extract. Such estimations 
of fat, however, are troublesome, and require much time for 
their performance. Thus far only a few such investigations 



UNUSUAL CONSTITUENTS IN THE URINE. 397 

have been made, and I know of none in which the quantity of 
fat separated in a definite time, say twenty-four hours, has been 
reckoned. Therefore, we have, thus far, no means of comparison. 

The following experiments, in the meantime, may serve to 
aid us : 

Kletzinsky found in the urine of different persons who suf- 
fered from Bright's disease the following quantity of fat in 
1,000 parts of urine : 0-24— 0-26— 0-28— 0-25— 0-37— 048— 1-27. 

Beale, on the other hand, found in one case 14 parts of fat in 
1,000 parts of urine. 

So-called chylous urine (see page 142) contains more or less 
fat in suspension, which gives it a milky appearance, and in 
addition to albumen, it frequently contains fibrine, and lymph 
and blood corpuscles. Lewis declares that at times there is a 
peculiar entozoon present also. (See § 118.) The discharge of 
such urine — called, also, galaduria — is only rarely observed in 
Europe ; on the other hand, it is observed with tolerable fre- 
quency in some of the tropical countries (East and "West Indies, 
Isle de France). It is not yet explained how this disease, 
which often lasts a long time, originates.* 

Kecently I had an opportunity, through the kindness of Dr. 
W. Harnier in Wildungen, to observe a very interesting case of 
well-marked galacturia, which originated, not in the tropics, but 
in Germany. The patient, a young man, for two years and a 
half had passed, almost without exception, a perfectly opaque 
urine of white color, which exactly resembled in appearance 
milk w^hich contains a good deal of fat. The turbidity depends 
wholly on fat, which is, for the most part, very finely granular, 
and only has a few large fat drops like those in milk. The 
urine is cleared up by shaking with ether, and an abundant 
residue of semi-fluid fat remains behind after the ether is evapo- 
rated. The urine, moreover, contains a large amount of fibrine, 
which coagulates partly after the urine is passed, and partly 
while still within the urinary passages, and in the latter case 
the coagula are sometimes large and can only be passed through 
the urethra with a good deal of trouble. The urine contains 
only a trace of albumen. When the patient fasts, and at the 

* Concerning this subject see, besides a tolerably copious foreign literature, 
Ackermann, Deutsche Klinik, 1863, 23, et seq., and Eggel, Deutscbes ArcMv f. 
klin. Med.-, vi., p. 424, 430. 



398 SEMIOLOGY OF HUMAN URINE, 

same time drinks mucli water, tlie milky cliaracter of his urine 
temporarily disappears. 

§ 102. Biliary Pigments. 

The bile pigments which occur in urine and the process re- 
quired to detect them have been studied in § 28. 

Importance. In rare cases traces of bile pigments have been 
found in the urine of persons in perfect health, particularly in 
the hot season of the year.^^ 

Bile pigments are found in large quantities only in jaundice 
(icterus), and after phosphorus poisoning. 

Their presence may be thus explained : The natural passage 
of the bile from the liver into the intestine being, for any reason, 
impeded or arrested, they get into the blood by absorption. The 
biliary pigments having been accumulated in the blood are sepa- 
rated from it with all of the secretions, but most jjarticularly 
with the urine. It is very doubtful whether a lorimarTj accumu- 
lation of bile pigments in the blood can occur, that is, whether 
they can pass directly into the urine from the blood without 
having previously formed a constituent of the bile. 

The idea originating with Frerichs, that the biliary pigment 
which is so abundant in icteric urine is derived partially from 
a decomposition of the biliary acids into biliary pigments in the 
blood, has not been confirmed. 

The presence of bile pigments in the urine has no great diag- 
nostic value, since we are usually able to recognize jaundice by 
other signs. In cases in which, owing to the slight yellow color 
of the skin, conjunctiva, etc., the diagnosis of jaundice is doubtful, 
the detection of the bile pigments in the urine may confirm it. 

Biliverdin and biliprasin generally prevail in the urine in 
jaundice. This indicates that the greater part of the biliary 
pigment in icterus undergoes a change during its absorption, 
or after it has reached the blood, or while it is passing into the 
urine. 

§ 103. Biliary Acids. 

The biliary acids which occasionally appear in the urine 
(cholic acid, glycocholic acid, choloidic acid, and their deriva- 

^ Scherer, Ann. d. Chem. u. Pliarm., Band 57, p. 180-195. 



UWUSUAL CONSTITUENTS IN THE URINE. 399 

tiyes, such as cliolonic acid), may be detected by the methods 
given in § 29 and § 83, and may be, at least approximately, de- 
termined quantitatively. 

Recently they have often been found in pathological urine, 
though always only in small quantity, especially in icterus and 
acute atrophy of the liver, by Klihne," Neukomm,t and Hoppe- 
Seyler.:]: Still their importance to the practitioner is slight, since 
it is rarely the case that important conclusions can be drawn 
from their presence or absence in reference to the diagnosis of 
a case of disease, or to assist in forming any other opinion con- 
cerning it. The presence of biliary acids in the urine is of prac- 
tical importance only by indicating an accumulation of these 
acids in the blood, which may be dangerous when it is consider- 
able, since they have a paralyzing influence on the nervous 
system, and more especially on the cardiac nerves. (Gerhardt.) 

In the meantime the following points may be mentioned in 
reference to this subject : 

Under normal conditions a considerable quantity of cholic acid 
is constantly being poured into the intestines with the bile. By 
far the greater part of it is absorbed again and passes back into 
the blood ; here the cholic acid is altered in a manner not fully 
understood, and disappears as such. If this change does not 
go on in the blood, so that the cholic acid accumulates there, 
then a portion of it may appear in the urine. As yet we do 
not know the conditions which prevent the disappearance of 
cholic acid in the blood, and favor its appearance in the urine. 
When Ave have learned these conditions better, we shall be able 
to determine fully the diagnostic and prognostic value of the 
presence of cholic acid in the urine. We may, however, de- 
duce a few conclusions from what is already known of these 
conditions as follows : 

It is not altogether inexplicable why we find, as a rule, only 
a little cholic acid in the urine in cases of icterus, where the 
urine is loaded with biliary coloring matters. When the flow 
of bile into the intestines is arrested, the bile pigment, whose 
normal avenue of exit from the body with the faeces is closed, 
must take an unusual course ; it is in part evacuated with the 

* Virchow's Archiv, 1858, p. 310, ei seq. 

\ Arcliiv f. Anat. und Pliys., 1860, p. 364, et seq. 

X Vircliow's Arcliiv, 1862, p. 1, et seq. 



400 SEMIOLOGY OF HTTMAN UBINE. 

urine. The cliolic acid, on the other hand, passes normally in 
great part back again into the blood and there disappears ; and 
since in icterus no change takes place in this respect, we can 
readily understand why, as a rule, in this disease we find much 
biliary pigment and little or no biliary acids in the urine. 

Moreover, as the disappearance of the biliary acids takes 
place in the blood and not in the liver, we should not, as a 
rule, expect to find them in diseases of the liver, but in those 
diseases of the blood in which the normal decomposition of the 
biliary acids in the blood is impeded or arrested. We might ex- 
pect that these acids would be found only in the urine in those 
diseases of the liver which are accompanied by an increase of 
the biliary secretion, and as the result of which so large a 
quantity of biliary acids accumulates in the blood that their 
normal transformation is not completely accomplished."^ 

§ 104. SUGAE. 

To detect sugar in the urine we must proceed according to 
§ 25, E. If the urine contains a large amount of sugar, its de- 
tection presents no difficulty to one who is a little skilled. The 
dark brownish-red color which saccharine urine assumes when 
treated with potassic hydrate and heated to boiling for a time 
is sufficient proof. The further test with sodic or potassic hy- 
drate and cupric sulphate, as well as the tests with bismuth 
and indigo-carmine, will serve to confirm it. 

Sometimes the urine also contains alkaiDton (see § 26) and 
brenzcatechin (see § 39). These cases, which are probably rare, 
and whose etiology is still unexplained, have no clinical im- 
portance, but they may lead to a false conclusion that sugar is 
present when this is not the case, from the great resemblance 
of the reactions caused by their presence in the urine to those 
caused by sugar. It is only by the reduction of nitrate, of bis- 
muth, the odor of caramel on boiling with potassic hydrate, 
and the fermentation test, that we can detect the presence of 
sugar in the urine when these substances are also present. t 

*For further particulars on this head, see Huppert (Archiv d. Heilk., 1864, 
p. 236, et seq.), and Ernst Bischoff (Henle u. Pfeuffer's Zeitschr. f. rat. Med., 
1864, p. 125, et seq.). 

■\ Compare Dr. P. Fiirbringer, Berliner klinische Wochenschrift, 1875, No. 34. 



UNUSUAL CONSTITUENTS IN THE UBINE. 401 

In cases where the tests above mentioned give no decisive 
results, we may be sure that the urine in question contains no 
very considerable quantity of sugar, and this suffices almost 
always for the purposes of the physician. Occasionally, how- 
ever, we may wish to know whether in such a case the urine is 
perfectly free from sugar or not, and whether it contains a very 
small quantity, or a mere trace of it. To answer this question 
with certainty is difficult and requires time. We must then em- 
ploy all of the precautions which have been described on page 
109, et seq. (preparation of an alcoholic extract of the evaporated 
urine, of a saccharate of potassium, etc.). 

To obtain an accurative quantitative analysis of the sugar in a 
specimen of urine, we must proceed according to § 70. The 
methods of analysis described there, however, are rather com- 
plicated, with the exception of the optical method, and cannot, 
therefore, be easily employed by the j)hysician, but, as a rule, 
must be entrusted to the chemist. In order to learn accurately 
the progress of the secretion of sugar, we must ascertain the 
quantity of sugar formed in a given time (x grms. of sugar in 
an Jioiir, for example, etc.). 

Comparative trials of the accuracy of the different methods 
employed to determine quantitatively the sugar in the urine 
(the oxide of copper test, fermentation test, and that by means 
of the polariscope) have been made by Wicke and Listing."' 

Attempts have also been made to determine the quantity of 
sugar in diabetic urine from the specific gravity, and for this 
purpose tables have been drawn up which are said to show how 
much sugar urine of a certain specific gravity contains. This 
method is quite extensively used in England, but is very inaccu- 
rate and cannot be employed even for approximate determina- 
tions, as Bence Jones t has shown. 

On the other hand, W. Manassein X found that Koberts' method 
of determining the quantity of sugar from the difference in the 
specific gravity of the urine before and after fermentation gave 
quite serviceable results. (Compare page 277.) 

Since the methods of determining the quantity of sugar in 
a specimen of urine as described above are difficult and tedious, 

« Henle u. Pfeuffer's Zeitsclir. , Neue Folge, Bd. 6, Heft 3. 
f Med. Times and Gazette, Feb. 4, 1854. 
•JDeutsches Archiv f. klin. Med., 1873, x., p. 73. 
26 



402 SEMIOLOGY OF HUMAN URINE, 

I have frequently employed another process instead, which is 
quite sufficient for the purposes of the physician, who, as a rule, 
only wishes to know about how much sugar a diabetic urine con- 
tains, and more especially whether the quantity has increased 
or diminished. This process is founded on the fact that saccha- 
rine urine when boiled with potassic hydrate assumes a yellow- 
ish-brown €olor, and that from the intensity of this color the 
quantity of the sugar may be determined by the aid of a color 
scale in the same way that the coloring matter of the urine is 
determined. 

The best way is to proceed as follows : A weighed amount 
(about 2 grm.) of well-dried grape sugar is dissolved in 40 or 
50 €C. of water, about double its volume of a tolerably concen- 
trated solution of potassic hydrate is added, and the mixture 
boiled 10 or 15 minutes. After cooling, the fluid, which has 
become dark brown, is treated with water until 1 cc. of it corre- 
sponds to 10 mgrm. of sugar. From this original fluid a scale 
of colors is prepared. For not very exact investigations a scale 
of a few members is sufficient, and we may use ordinary test 
tubes of as nearly as possible equal diameter. We fill the first 
one with a fluid consisting of one part of the original fluid and 
nine parts of water, so that 10 mgrm. of sugar are contained in 
10 cc. of the fluid. The second tube is half filled with the fluid 
first used and then an equal quantity of water is added; we 
then obtain a member of the scale in which 5 mgrm. of sugar 
are contained in 10 cc. A third, fourth, and fifth test tube are 
filled with fluids, 10 cc. of which correspond to 3, 2, and 1 
mgrm. of sugar respectively, etc. If we prepare a scale of 10 
or 12, members, and select large glasses of as nearly equal dia- 
meter as possible and having a capacity of h to 1 lb., we can 
arrive at a very accurate determination. "When we have pre- 
pared such a scale, a measured quantity of the urine to be 
tested is boiled (when the urine is very saccharine 5 cc, when 
it contains but a little sugar 10 cc.) with double its volume of 
a solution of potassic hydrate ; after cooling it is placed in a 
glass vessel corresponding in form and size to those of the scale, 
and water is added to it until its color corresponds to that of one 
of the members of the scale. We may now from the known quan- 
tity of the sugar contained in that member of the scale very 
readily reckon the quantity of sugar in the urine. This method 



UNUSUAL CONSTITUENTS IN THE URINE. 403 

is very convenient (it requires only a few minutes to perform it), 
and is, therefore, especially adapted for clinical purposes. Tlie 
scale itself does not keep long, it is true, but the original fluid 
wlien preserved in a cool, dark place may be kept a long time, 
and a new scale may be quickly prepared from it. In the rare 
cases in which the urine contains large quantities of alkapton 
or brenzcatechin (see page 400), this method is naturally not 
applicable, since these substances also color the urine bxow-n 
when treated with potassic hydrate. 

Importance^ It is still very difficult at present to explain tlie 
cause of the occurrence of sugar in the urine. It, therefore, 
appears advisable to keep in mind the facts which are of most 
importance to the practitioner. 

From the standpoint of the phy-sician two points are to be 
discriminated : 

1. In the one case the urine not only contains sugar in large 
quantities, but it is for a long time constantly present (only when 
fasting do ,such persons sometimes pass a urine which is iree 
from sugar.) 

2. In the other case the urine contains only traces of sugar, 
or the sugar is present merely temporarily, or for a short time, 
or contains a <jonsiderable amount intermittently with intervals 
when it is absent. 

In the first case we may conclude that the disease known 
as diabetes mellitus, glycosuria, is present. There are then 
usually other symptoms present which serve to assist us in 
' making the diagnosis and prognosis : a very large quantity of 
urine of high specific gravity, great thirst, emaciation, dryness 
of the skin, etc. This is not the place to enter into a detailed 
description of the nature, cause, progress, and complications of 
diabetes mellitus, and I may remark here, that in all such cases 
the physician is justified in making, if not an unfavorable, afc 
least a very doubtful prognosis. 

The prognosis is frequently more favorable in those cases in 
which the evacuation of a saccharine urine has been observed 
after injuries of the brain, similar to those which are caused by 
the so-called sugar-puncture in animals, provided, naturally, 
that the injury to the brain does not of itself demand a bad 
prognosis. 

The second case, in which the urine contains only traces of 



404 SEMIOLOGY OF HUMAN URINE. 

sugar, or, only occasionally, large amounts of it, is observed 
in the course of several different diseases, and even in per- 
fectly healthy persons. The cause of it has hitherto been at- 
tributed to various conditions by different physiologis-ts : to an 
immoderate use of saccharine and amylaceous substances, to 
disturbances of the functions of the brain and nervous sys- 
tem, especially of the medulla oblongata, to diminution of the 
respiration and absorption of oxygen, to excessive production 
of sugar by the liver, and to a diminution of the alkalies in the 
blood. It is always advisable for the physician in such a case 
to direct his attention to these etiological conditions and to as- 
certain whether any one of them is present, and to govern his 
therapeutics accordingly. But a perfectly satisfactory explana- 
tion and treatment of such a case Avill only be possible in the 
future, when the causes mentioned, which are still partly under 
discussion, shall be more accurately determined and their in- 
fluence on the elimination of sugar with the urine shall be more 
perfectly known than is the case at present. In the meantime 
the following seems to be the most probable vieAv : When from 
any cause a greater quantity of sugar accumulates in the blood 
than can be decomposed in it by the process of metamorj^hosis 
— whether it be that an unusual quantity of sugar gains access 
to the blood, or that its decomjDosition in the blood is hindered 
in any way — a part of the excess may be passed off with the 
urine, just as is the case with many other substances. 

Under this head belongs the jDresence of small quantities of 
sugar in the blood of the arteries, veins, portal vein, in the 
urine of pregnant, lying-in, and nursing women, and also in the 
urine of perfectly healthy men. After much controversy in 
this matter it now appears tolerably certain from the investi- 
gations of Briicke and Iwanoff, and contrary to the assertion of 
Seegen (see page 101), that the urine of healthy persons even 
sometimes contains small quantities of sugar. Such investiga- 
tions, however, have little value for the practitioner from a 
diagnostic point of view ; they rather concern the chemist and 
physiologist. It is still very difficult to obtain reliable results 
in this matter, since in investigations of this sort only the most 
exact methods of procedure and the purest reagents will enable 
us to exclude errors. Then, too, no one should experiment in 
this direction without a perfect mastery of the literature of the 



UNVSUAL CONSTITUENTS IN THE URINE. 405 

subject, which has already become quite extensive. The two 
comprehensive treatises of Lehmann,^ and the dissertation of 
NicoL Iwanoffjt which contains the latest literature of the sub- 
ject, will best serve to give a general idea of the matter. 

According to De Sinety:}: sugar occurs in the urine of pregnant 
women and in lying-in women only when the lacteal glands 
are imperfectly emptied, when it regularly occurs. Conse- 
quently sugar is always found in the urine on the second or 
third day after delivery at the time of the milk fever. The 
secretion of milk at this time is quite abundant, while the child 
gets but little of it. The urine may be rendered saccharine at 
will in nursing dogs and rabbits by removing the young. The 
increase of sugar in the blood could be detected when the milk 
was not removed. 

Sugar has sometimes been observed in the urine after having 
taken oil of turpentine (see page 102), also temporarily in teta- 
nus rheumaticus§ and in persons suffering from intermittent 
fever. il 

According to the investigations of L. Senff,l the urine of 
animals temporarily (two or three hours) contains sugar after 
they have been made to inhale carbonic oxide. 

Ewald''^"^ brought on glycosuria in rabbits and dogs by inject- 
ing nitrobenzol. 

Kiilz tt also succeeded in producing glycosuria in dogs and 
rabbits by injecting various substances. 

Inosite (compare § 27) has been found in the urine repeatedly 
of late, but always only in pathological cases, sometimes ac- 
companied by grape sugar, sometimes with albumen in nephri- 
tis albuminosa. Its source and importance are still unknown. 



* Schinidt's Jahrb., Band 87, p. 281, and Band 97, p. 3, 6^ seq. 

f Beitrage zu der Frage liber die Glycosurie der Scliwangeren, Wochnerinnen 
und Saugenden, Dorpat, 1861. 

\ Recherches sur I'urine pendant la lactation, Gaz. med. de Paris, 1873, No. 
43 and 45. 

§ A. Vogel, Deutsches Arcliiv f. kiln. Med., 1872, x., p. 103. 

I E. Burdel, De la Glycosurie ephemera dans les fievres palustres, Union 
med., 1872, Nro. 105, p. 368, et seq. 

*f Inaugural-dissert. , Dorpat, 1869. 

*^ Centralblatt f. d. med. Wissenscb., 1873, Nro. 52. 

f f Beitrage zur Hydrurie und Melliturie, Habilitationsscbrift, Marburg, 
1872. 



406 SEMIOLOGY OF HUMAN TJBINE. 

It appears, liowever, to come from the glycogen of the liver, 
for in puncture of the fourth ventricle of the brain in animals 
or in a corresponding organic disease of the brain inosuria is 
sometimes produced instead of glycosuria. 

Cases of inosuria are described by Gallois,"^ Schultzen,t and 
others. 

Inosite was also detected in the urine in a case of polyuria 
with softening of the medulla described by Mosler.J 



A few other substances which have been found in the urine 
in isolated cases, such as lactic acid (see § 30), various vola- 
tile fatty acids (see § 31), benzoic acid (§ 32), which occurs only 
in decomposing urine, sulphuretted hydrogen (§ 34), allantoin 
(§'*35), have at present so little practical significance that a dis- 
cussion of them here is unnecessary. We shall speak of cer- 
tain substances later, as leucin, tyrosin, etc., when they occur 
under circumstances which are of interest to the practitioner. 
(§ 112 and § 133.) 

§ 105. Accidental Abnormal Constituents. 

Under this head are comprised various, unusual constituents 
of the urine which are derived from the food, drink, medicines, 
etc., and which pass into the urine either changed or unchanged, 
thus rendering it abnormal, but without the abnormity having 
a pathological significance. 

We have already in different places spoken of these accidental 
constituents of urine, their detection and signification. (§ 56, 
p. 190, etc.) They are of more special interest to the chemist 
and physiologist : to the former^ because they acquaint him 
with many products of the decomposition of complex organic 
substances ; and to the latter, in explaining changes which dif- 
ferent substances undergo in the human and animal economy, 
and thus throw light on many points concerning the inter- 
mediate metamorphosis of tissue. 

Among these substances which occasionally appear in the 
urine, and which are, at present at least, of more interest to 

* De rinosurie, Paris, 1864. 

\ Arcli. f. Anat., 1863, i., p. 23, et seq. 

X Yircliow's Archiv, 1873, Ivi., p. 44, et seq. 



UNUSUAL CONSTITUENTS IN THE URINE, 407 

chemists and physiologists than to practitioners, are to be con- 
sidered small quantities of nitrates and nitrites (see § 21), which 
doubtless come from the food and drink consumed, and also 
small quantities of peroxide of hydrogen (see § 22). Both were 
first detected by Schonbein."^ 

But they have also some importance for the physician, and 
in time will assume a still greater one. From their presence 
we may learn that a patient has taken certain food,, drink, or 
medicine. Thus asparagus, oil of turpentine, saffron, cubebs, 
etc., betray themselves by the odor which they impart to the 
urine ; many vegetable substances, as rhubarb, senna, certain 
roots and fruits containing pigment, sometimes also creosote, 
tar, and santonin (see page 368), when taken internally, betray 
their presence by coloring the urine ; while other substances 
which pass into the urine may be detected by a chemical exami- 
nation. 

It is still more important to the physician to know whether 
certain medicines are eliminated with the urine, and if so, in 
what quantity, since the answer to this question frequently 
determines whether a patient shall continue the use of such 
remedies or omit them. (See page 358). 

In many cases of poisoning, also, the poison may be detected 
in the urine, and the examination of the latter may be of im- 
portance at times in forensic medicine as well as in reference 
to diagnosis and treatment. 

The following bodies are those whose detection in the urine 
is of especial interest to the physician : 

The methods of detecting their presence are often quite com- 
plicated, therefore an accurate description here would take up 
too much space, t 

Lead sometimes passes into the urine after lead poisoning 
and after the therapeutical use of preparations of lead. Its 
detection, however, is difficult and is not always successful, t 

Copper may generally be found in the urine after poisoning 
by copper. (Kletzinsky.) 

* Journ. f. prakt. Chemie, 1864, p. 152, et seq., and p. 168, et seq. 

f See § 56, and tlie ttiorougli treatise of Kletzinsky, Wiener medicin, Woch- 
enschr., 1857 and 1858. Also MayenQon and Bergeret, Journ. de I'anat. et de 
physiol., 1872, Nro. 80-98 ; 1873, Nro. 3. 

I See also Folwarczny, Wiener Zeitschrift, N. f., ii., b. 1859. 



408 SEMIOLOGY OF HUMAN UBINE. 

It may be of interest to the pliysician to detect the presence 
of mercury in the urine in mercurial poisoning and after mer- 
curial treatment. In the latter case we may wish to know 
whether the mercury still exists in the economy, or whether it 
has already been eliminated. For the methods of proving this 
see page 192. 

Salts of zinc pass readily into the urine, and may be detected 
in it without difficulty. (Kletzinsky.) 

NicJcel and cobalt, both of which, especially the former, have 
a poisonous action, may be recognized in the urine. 

Arsenic and antimony also pass into the urine, and may be 
detected in it by the familiar processes by means of Marsh's ap- 
paratus. 

The detection of iodine in the urine, after its exhibition, may 
sometimes interest the physician by indicating to him whether 
the economy still contains iodine or not. The amount of iodine 
in the urine may be very accurately determined quantitatively. 
(See page 197, and § 71.) The same is true of bromine. (See 
page 197.) 

After the internal administration of the carbonates of the alka- 
lies or vegetable alkaline salts (acetates, etc.) given as diuretics or 
to neutralize an excess of acid in the urine, it is often important 
for the physician to have a means which will enable him to de- 
termine how long such remedies may be given without injury, 
and when they shall be omitted, and when continued. In such 
cases the chemical reaction of the urine forms the best indica- 
tion. As long as the urine has an acid reaction such remedies 
may be continued without injury, the system is not yet satu- 
rated with them. 

If, however, the urine has a distinctly alkaline reaction, not 
from the presence of carbonate of ammonium, but from an ex- 
cess of fixed alkalies (see page 377, b), it is best in most cases 
to omit the remedy, and to allow it to be repeated only after 
the urine has become acid again. The exhibition of these 
remedies should occur during the time when the stomach is 
empty, because during the two or four hours which follow a 
meal the urine is less acid, and sometimes even alkaline. (See 
§ 127.) 

Tannic acid passes into the urine as gallic or pyrogallic acid. 

Alcohol, carhoUc acid, and chloroform appear in the urine, and 



URINARY SEDIMENTS. 409 

may be detected in it according to tlie methods mentioned in 
§56. 

The greater part of quinine which has been absorbed, appears 
relatively soon in the urine again. By far the greatest part is 
eliminated in the first twelve hours after its exhibition in 
healthy persons, and in those suffering from fever ; but in the 
latter, the chief part of the elimination takes place during the 
second six hours. "^ For the process of detecting quinine in the 
urine, see page 204 

lY. URINARY SEDIMENTS. 

§ 106. 

By urinary sediments is meant the occurrence of solid sub- 
stances insoluble in the urine, which, at first, are usually sus- 
pended in it, and after a longer or shorter time sink and form 
a sediment. The deposit forms more rapidly and completely 
the coarser and heavier the solid particles in suspension are, 
and more slowly and incompletely the finer and lighter they 
are. 

Slight sediments, consisting of very small molecules, which 
subside only with difficulty, and on shaking are very readily 
dispersed again, are only recognizable by a cloudy appearance 
and diminished transparency of the urine, and are called 
turbidities (clouds — nubeculse). Sediments which consist of 
large particles distinctly visible to the unaided eye, like small 
grains of sand, are called urinary sand or gravel. 

Urinary sediments give important information to the phy- 
sician, and frequently enable him to recognize at once cer- 
tain changes of the urine, which would otherwise often require 
a very tedious chemical investigation. Sometimes, indeed, a 
chemical test is necessary to determine the nature of a sedi- 
ment, still more frequently a microscopic examination is re- 
quired, and urinary sediments are among the objects for the 
accurate diagnosis of which a conscientious physician frequently 
requires the microscope. 

The semiotic importance of urinary sediments is, like that of 
the urine, a double one. 

1. They give information concerning certain changes in the 

*^H. Thau, Deutsches Archiv f. klin. Med., v., p. 505, et seq. 



410 SEMIOLOGY OF HUMAN URINE. 

general metamorphosis of tissue in disease. They teacli the phy- 
sician that an unusually large quantity of certain substances is 
separated with the urine, and, therefore, must be produced in 
the system; as, for example, hippuric acid, oxalic acid, etc. 
By their aid we are often able at a glance to learn much, fre- 
quently with absolute certainty, sometimes indeed only with 
probability, which is of value to the practitioner, and which 
the chemist in determining must attain by troublesome investi- 
gations. 

2. They indicate to us certain local diseases of the uropoetic 
system. Thus, the presence of a purulent sediment indicates 
suppuration in some part of the urinary apparatus; urinary 
casts indicate certain morbid changes in the parenchyma of 
the kidney ; the chemical composition of gravel points out the 
probable composition of urinary calculi whose presence has 
been recognized by other means. 

Some urinary sediments form before, and some after the 
urine has been passed; the former may give rise to urinary 
calculi under favorable circumstances, whereas the latter natu- 
rally cannot. For this reason, in many cases it is of practical 
importance to determine whether a sediment already existed in 
the urine when it was passed, or whether it formed in it after- 
ward. 

After these general considerations concerning urinary sedi- 
ments, we will turn our attention to the importance of the indi- 
vidual constituents. 

A. Non-Organized Sediments. 

Sediivients of Uric Acid and Urates. 
§107. 

Sediments consisting of uric acid and urates occur very fre- 
quently in the urine ; especially in acute febrile diseases, this 
variety of sediment occurs much more frequently than all of 
the other sediments taken together. 

For their detection, see § 43 and § 44. 

The conditions of their formation are, as a rule, complicated, 
and it is often difficult in any given case to determine how far 
one or the other of the causes mentioned below is active. 



URmARY SEDIMENTS. 411 

Uric acid is one of the normal constituents of urine, but it is 
soluble in it only with difficulty, and in small amount. When, 
therefore, changes in the urine occur which bring about such a 
condition that all of the uric acid contained in it cannot be re- 
tained in solution, the portion not dissolved is separated as a 
sediment. 

These changes of the urine, which accompany the formation 
of uric acid sediments, may be divided into two groups, whose 
differentiation is of great practical importance : 

1. The quantity of uric acid which passes into the urine in a 
given time (one hour, twenty-four hours) is greater than usual. 

2. But if the urine secreted contains less water than usual, 
or in other words is very scanty, a uric acid sediment may 
be formed without the absolute secretion of uric acid being 
greater than usual. 

A uric acid sediment in the urine, therefore, is not, as many 
physicians appear to believe, proof that there is an absolute 
increase in the quantity of uric acid formed and secreted. 
Such a conclusion is only justifiable when we have ascer- 
tained, according to § 73, and quantitatively determined the 
amount of uric acid passed within a given time (a known num- 
ber of hours), and have found that it is greater than normal. 

The causes which give rise to the formation of uric acid sedi- 
ments are usually the following : 

1. The urates are much more soluble in" hot water than in 
cold. Consequently urine which is nearly saturated with these 
salts at the temperature of the human body throws down a 
sediment of urates on cooling. We frequently see, therefore, 
urine, which is perfectly clear on being passed, become cloudy 
from a separation of the urates, when it has lost the tempera- 
ture of the body and become cool. 

It is evident that urate sediments cannot easily occur in this 
way within the body during life, because the urine can never, 
except in the very rarest cases, undergo the necessary degree 
of cooling within the body. But it may happen that urine 
saturated with urates may undergo a further concentration in 
the urinary passages by endosmosis, so that a portion of its 
urates are rendered insoluble and precipitate, and thus form a 
sediment in the urinary passages ; such a case, however, appears 
to occur but very rarely. 



412 SEMIOLOGY OF HUMAN URINE, 

2. The normal urates are more soluble tlian the acid salts, 
and the acid salts are more soluble than free uric acid. Con- 
sequently a sediment is formed whenever the normal salts in 
the urine containing them in large quantity are from any cause 
converted into acid salts or free uric acid. 

We see this change occur out of the body during the acid 
fermentation. Uric acid sediments may be formed Avithin the 
body for the same reason by either an acid fermentation of 
the urine, or a mutual decomposition of the urates and the 
aoid j)hosphate of sodium, as has been already described in 
§ 42, or when a very acid urine by a change in the secretion 
is mixed with the urine already in the bladder which is but 
slightly acid or even alkaline, in which case the acid urine ab- 
stracts the base from the normal urates either wholly or in 
part. 

It is probable that the fermentation of the urine may also 
occasion uric acid sediments in other ways than by the forma- 
tion of acid. The urinary pigments, indeed, appear to aid ma- 
terially in the solution of uric acid in the urine. Consequently 
if the urinary pigment is partially altered and decomposed by 
the fermentation, a portion of the urates will be precipitated 
from the urine. 

So much for the theory of the formation of these sediments : 
we will now turn to their practical importance. 

Sediments of urates most frequently occur in acute febrile 
diseases or in febrile exacerbations of chronic diseases. In 
such cases almost always several of the above-mentioned pre- 
disposing causes act at the same time : diminution of the watery 
part of the urine, and consequently of the whole amount of 
urine, absolute increase of the uric acid, strongly acid urine, 
and a large amount of pigmentary matter in it. The sediment 
in such cases usually appears some little time after the urine 
has been passed, and its occurrence is caused partly by the 
cooling of the urine and partly by the commencement of urinary 
fermentatation and decomposition of the pigment matters, in 
which such febrile urines usually abound. 

The appearance of such sediments varies very much ; some- 
times they are of a clay color, sometimes brick red, rose or 
cinnamon colored — under the microscope they usually appear 
finely granular. They usually consist of normal or acid urates 



UBINARY SEDIMENTS. 413 

whose base is soclmm, potassium, or ammonium, more rarely 
calcium. (For their separation, see § 44.) 

Their simplest diagnostic mark is, that the turbid urine con- 
taining them becomes clear on being heated and the turbidity 
returns on cooling. 

Their importance consists in indicating that certain changes 
of metamorphosis occur in most febrile diseases (increased for- 
mation of uric acid and of pigment, together with diminished 
secretion of water with the urine). They are frequently re- 
garded as critical. There is reason in this, in so far as the 
separation of an excess of uric acid from the blood may be a 
favorable sign, while a retention of it in the blood would pro- 
duce evil consequences. They have, however, very often de- 
cidedly no critical significance, for we frequently see that the 
chief symptoms of the disease continue unabated for a long 
time after their appearance. 

Sometimes such sediments appear in perfectly healthy per- 
sons when the above-mentioned conditions are present : they 
occur, for example, after violent bodily exercise, excessive eat- 
ing, profuse perspiration with consequent diminution in the 
amount of urine ; also after a night of revelry or a fatiguing ex- 
cursion on foot in the heat of summer. 

Since such sediments are almost always formed outside of 
the body, they only exceptionally give rise to the formation of 
urinary concretions. 

It is of no practical importance to determine the base with 
which the uric acid is combined in such sediments, that is, 
whether the sediment consists of urate of sodium, potassium, 
ammonium, or calcium. 

The urine more rarely contains sediments of uric acid. These 
usually occur in large crystals, often apparent to the unaided 
eye, or in the form of crystalline masses, sometimes alone, some- 
times imbedded in a sediment of urates. Such sediments may 
arise when the urine becomes acid from one of the above-men- 
tioned causes, and every sediment of urates may be artificially 
converted into a crystalline sediment of uric acid by the addi- 
tion of an acid. 

In this case it is important to ascertain whether the sediment 
has formed after the urine has been passed, or whether it al- 
ready existed in the urinary passages, the kidneys, or bladder. 



414 SEMIOLOGY OF HUMAN URINE. 

Tlie latter is quite important, practically, because by its long 
continuance we have reason to fear that uric acid calculi may 
be formed in the kidneys or bladder of such a j)atient. 

§ 108. HiPPURic AciD.^ 

We consider hippuric acid under the head of sediments, be- 
cause it usually appears as a sediment in those cases which 
interest the physician, and because in this form it is more easily 
and quickly recognized by means of the microscope than chemi- 
cally by evaporating the urine, etc. (See § 8.) 

Sediments of hippuric acid are relatively rare ; under the 
microscope they usually appear as rhombic prisms, and some- 
times in the form of needles. (Plate I., fig. 1.) They may be 
confounded with uric acid crystals or crystals of ammonio-mag- 
nesian phosphate. They may be easily distinguished from the 
latter by their insolubility in hydrochloric acid ; and from the 
former by not giving the murexide reaction characteristic of 
uric acid. Sometimes a sediment consists of a mixture of uric 
acid and hippuric acid crystals, and I have occasionally seen 
needle-shaped crystals of hippuric acid attached like spears to 
large crystals of uric acid. In cases of this kind it is best to 
collect the sediment on a filter and then to boil it in alcohol. 
This dissolves the hippuric acid only and leaves the uric acid 
undissolved. By evaporating the alcoholic solution we obtain 
the hippuric acid isolated, in the form of crystals, which may 
be more carefully tested and determined in the manner de- 
scribed in § 8. 

An adequate number of investigations as to the amount of 
hippuric acid in normal urine, and its variations is not yet at 
our command. According to those which have been published 
thus far, the average quantity of hippuric acid in the urine 

* W. Ducliek, Das Vorkommen der Hippursaure im Harn des Mensclien, 
Prager Vierteljalirsclir,, 1854, Band 3, p. 25, et seq. W. Hallwaclis, Ueber den 
Ursprung der Hippursaure im Harne der Pflanzenfresser, Ann. d. Chem. und 
Pliarm., 1858, Band 105, p. 207, et seq. R. Wreden, Quantitative Bestimmung 
der Hippursaure mittelst des Titrirverfalirens, .Tourn. f. prakt. Chemie, 1859, 
Band 77, p. 446. A. Liicke, Ueber die Anwesenbeit der Hippursaure im mensch- 
licben Harn und ibrc Auffindung, Vircbovv's Arcbiv, 1860, Band 19, p. 196. 
J. L. W. Thudicbum, Researcbes on tbe pbysiolog*. variations of tbe quantity 
of bippuric acid in buman urine, Journ. of tbe Cbem. Society. * 



JJRmABY SEDIMENTS. 415 

passed in twenty-four hours, by persons in health, amounts to 
fi'om 0*17 to 1 grm., but after eating largely of those substances 
mentioned below, it rises much higher (to over 2 grm.). For 
further particulars see pages 47, 48. 

According to Lawson the urine of the inhabitants of tropical 
countries, at least in Jamaica, is unusually abundant in hippuric 
acid. 

The causes which determine the separation of hippuric acid 
as a sediment are quite the same as those mentioned under 
uric acid. 

Importance, Large deposits of hippuric acid occur in the 
urine of persons in perfect health after they have eaten largely 
of fruit, and particularly prunes (Duchek), bilberries ( Vaccinium 
vitis idceajy and mulberries (Buhtis cJiamcemorus) (Liicke) ; also 
after taking benzoic and cinnamic acids, which are converted 
into hip|3uric acid in the body, and as such separated from the 
urine. 

The statement of Kiihne, that after the ingestion of succinic 
acid a large quantity of hippuric acid appears in the urine, could 
not be confirmed by Hallwachs, Liicke, and Meissner. 

When the physician finds a large amount of hippuric acid in 
the urine of sick people, he must first of all ascertain whether 
it depends on any such cause (as the ingestion of fruit or ben- 
zoic acid). Yet, without doubt, a large amount of hippuric acid 
may be found in the urine, caused by morbid changes of the 
metamorphosis. Thus, hippuric acid has been found in large 
quantities in the acid urine of fevers, in which, indeed, it has 
been the chief source of the acid reaction (Lehmann) ; it has 
also been found in diabetes, chorea, etc. The observations, how- 
ever, hitherto made concerning the presence of hippuric acid in 
the urine of the sick, are still very imperfect, and furnish nothing 
of value for the diagnosis, prognosis, and treatment of such cases. 

The opinion that a tendency to the excessive formation of 
uric acid may be removed by the use of benzoic acid, in con- 
sequence of the uric acid in such a case being replaced by 
hippuric acid (Ure, Keller), has been proved to be erroneous, 
and at the same time the proposed administration of benzoic 
acid as a remedy in the uric acid diathesis is seen to be of no 
practical value. 

During the last few years a large number of investigations 



416 SEMIOLOGY OF HUMAN TJRINE. 

have been carried on with respect to the sources of hippiiric 
acid in the urine both of human beings and of herbivorous 
animals, by which it is much more plentifully excreted.*^ But 
they have thus far yielded no results which could be practically 
utilized by the physician. Yet it seems probable that the biliary 
acids, and consequently the liver indirectly, by their formation 
in the body play some part.f 



§ 109. Eaethy Phosphates. 

(Phospliate of Calcium and Ammonio-magnesian Phospliate [Triple 
Phosphate].) 

Earthy phosphates very frequently occur in urinary sediments 
and chiefly in chronic diseases and in alkaline urine, the reverse 
of the case with uric acid sediments. When the urine is alka- 
line they are never absent, whether the alkalinity is spontane- 
ous or has been occasioned artificially by supersaturation of 
the free acid of the urine with caustic alkali or alkaline car- 
bonate. 

Its mode of origin is thus explained : When urine is rendered 
alkaline by the formation of carbonate of ammonium resulting 
from the decomposition of urea (compare § 96 and j)age 161), 
not only is its phosphate of calcium precipitated, being soluble 
only in acid fluids and not in alkaline ones, but it also forms 
by the action of the ammonia on the phosphate of magnesium 
always present in the urine, a triple phosphate of ammonio- 
magnesian phosphate, which separates, since it is insoluble in 
alkaline fluids. Since now all urine, with very rare exceptions, 
contains both phosphate of calcium and phosphate of magne- 
sium, the alkaline fermentation produces a sediment in every 
urine consisting of a mixture of both of these earthy phos- 
phates. 

This sediment, according to Neubauer's numerous investiga- 
tions,:}: contains on the average 67 parts of phosphate of magne- 

* Besides the ahove literature, see especially E. Lautemann, Ann. d. Chemie 
und Pharm., 1863, p. 9, et seq., and Meissner and Shepard, Untersuchungen 
iiber das Entstehen der Hippursaure, Hannover, 1866. 

f See Baumstark, Berliner klin. Wochenschr., 1873, Nro. 4. 

J Journ. f. prakt. Chem., Band 57, p. 65, et seq. 



TIBmART SEDIMENTS. 417 

sium and 33 parts of pliospliate of calcium in 100 parts. (Com- 
pare also § 132.) 

See § 46 for an account of tlie chemical and microscopic char- 
acters of this sediment. The triple phosphate is always dis- 
tinctly crystalline, and its crystals are usually very well formed 
and shaped like a coffin lid (Plate II., fig. 3, 5, and 6) ; more 
rarely (only when it is freshly precipitated) it is less perfect, 
but even then its groups of crystals are none the less character- 
istic and closely resemble two fern leaves crossing each other 
at an acute angle. 

Phosphate of calcium, on the other hand, usually appears 
amorphous under the microscope, in ill-defined, highly trans- 
parent flakes or cell-like spheres, only occasionally crystalline. 
(See page 169.) Frequently they are so transparent and their 
contour so badly defined, that some little practice is required 
to recognize them under the microscope. This is the reason 
why such sediments when examined microscopically so fre- 
quently appear to consist of triple phosphate alone, while, as a 
rule, one-third at least consists of phosphate of calcium. 

The case is different when the alkaline condition of the urine 
does not depend on carbonate of ammonium, but on carbonate 
of potassium, sodium, or some oilnQV fixed alkali. Then no triple 
phosphate can form, and the sediment appears to consist only 
of phosphate of calcium. 

Sometimes, however, crystalline deposits of phosphate of 
calcium without triple phosphate are formed even in faintly 
acid urine."' 

A. Eiesell found a sediment of phosphate of calcium in the 
urine, which had already formed within the urinary passages, 
after the long-continued administration of chalk. 

Importance. It was formerly the idea that sediments of the 
earthy phosphates were usually associated with an excess of 
these substances in the urine, and such cases were considered 
as so-called phosphatic diathesis. This is wholly erroneous: 
for every urine which is alkaline, and especially if it is ammo- 
niacal, contains a sediment of the earthy phosphates, so that a 
sediment of this kind does not by any means indicate an abnor- 

* Hassall, On tlie frequent occurrence of pliospliate of calcium in tlie crystal- 
line form in human urine, and on its pathological importance. Proceedings of 
the Royal Soc, x., 38, 1860, p. 281. 

27 



418 SEMIOLOGY OF HUMAN XmiNE. 

mally increased amount of earthy phospliates in tlie xirine. An 
increase of the earthy phosphates can only be proved by a 
quantitative determination of their amount. (See § 76.) At most 
^e can only give an approximate idea of the amount of earthy 
3)hosphates in a specimen of urine from the quantity of the 
sediment ; according to § 91, however, this last process requires 
much practice and is not very trustworthy. 

Independently of this approximate determination of the 
amount of earthy phosphates these sediments have a practical 
importance. 

1. They are usually the first to indicate to the physician that 
there is an alkaline condition of the urine with its consequences, 
and to prompt him to investigate its cause more carefully. (See 
§ 96, especially page 377.) 

2. In those cases in which the freshly passed urine already 
contains a sediment of earthy phosphates, it is evident that 
they must have been formed within the urinary passages, and 
consequently we may have reason to fear that they may give 
rise to the formation of phosphatic calculi, if this condition 
lasts a long time. 

§ 110. Oxalate of Ijime. Calcic Oxalate.- 

Calcic oxalate is of especial importance to the physician as 
a urinary sediment, because in this form it is much more easily 
and quickly recognized by the aid of the microscope than by 
chemical analysis. We shall, therefore, consider here all of 
the different circumstances which have a bearing on the occur- 
rence of this substance in the urine. 

To recognize a sediment of calcic oxalate quickly in the 
urine, it is best to use tolerably high powers of the micro- 

*F. \Y. Beneke, Zur PhysiologieTind Patliologie des pliosphorsauren und oxal- 
sauren Kalkes, Gottingen, 1850. Ibid., Zur Entwicklungsgeschichte der Oxa- 
lurie, Gottingen, 1852. James Begbie, On Stomacb and Nervous Disorders as con- 
nected with the Oxalic Diathesis, Edinburgh Monthly Journal of Med. Science, 
August, 1849. Ch. Frick, in Baltimore, Remarques sur la diathese d'oxalate 
de chaux et sur son traitement, Gazette des hopitaux, 27 Septembre, 1849. 
Gallois, Mem. sur I'oxalate de chaux dans les sediments de I'urine, dans la gra- 
velle et les calculs, Gaz. med. de Paris, 1859, Nro. 35, et seq. Smoler, Studien 
liber Oxalurie, Prager Vierteljahrschrift, 18G1. M. Seligsohn, Centralbl. f. d. 
medic. Wissensch., 1873, No. 22, 27, 28, 33. 



URINARY SEDIMENTS. 419 

scope. Tlie sediment is always crystalline, to be sure, but the 
crystals, as a rule, are very small, usually much smaller than 
blood or pus corpuscles. The form of the perfect crystal is 
always that of an envelope (quadrilateral-octahedron, Plate I., 
fig. 3). The smallest, even under high powers, always appear 
only as angular points, and on account of this minuteness of 
the crystals it is usually impossible to recognize a urinary sedi- 
ment of calcic oxalate with the unaided eye. It is best when 
we suspect such a sediment to filter the urine, and to carefully 
scrape the precipitate from the filter while it is still moist. 
When it is placed under the microscope the practised eye will 
immediately recognize the crystals of calcic oxalate, as a rule 
mixed with epithelium, mucus, and fragments of fibres of the 
filter, and sometimes with other crystalline sediments, as for 
example uric acid. If the diagnosis is doubtful, the other tests 
for calcic oxalate given in § 45 will confirm it. 

By this method we can discover the slightest traces of calcic 
oxalate in the urine, and we cannot be more certain by chemi- 
cal means. Still, calcic oxalate may occur in solution in urine 
which contains no trace of sediment. (See page 165.) 

Causes and Importance. The' causes of the occurrence of cal- 
cic oxalate in the urine may be sought in the following facts : 

1. Oxalic acid and calcic oxalate form a constituent of many 
articles of diet in the vegetable kingdom (wood sorrel, com- 
mon sorrel, the familiar fruit of the Solanum licopersicum, 
known by the name of love apples), and of many medicinal 
agents. (Leaving out of account the occasional therapeutical use 
of oxalic acid and its salts, oxalates are contained in the root of 
rhubarb, gentian, saponaria, etc.) Oxalic acid gains entrance 
into the body in this way, and is separated again by the urine 
either wholly or in part as calcic oxalate. 

2. Oxalic acid is frequently formed as a secondary product 
by the decomposition of animal, vegetable, or mineral sub- 
stances. Thus it is formed by the oxidation of uric acid, 
kreatinin, leucin, etc. ; by the imperfect oxidation of sugar, 
starch, and salts of the vegetable acids, whereby these, instead 
of being wholly transformed into carbonates, become in part 
oxalates which contain less oxygen. It is, moreover, probable 
that oxalates may be formed from carbonates and bicarbonates, 
when a part of their oxygen is removed from them by a process 



420 SEMIOLOGY OF HUMAN URINE. 

of reduction. These facts in a measure explain why oxalic 
acid may be formed in the human system under favorable cir- 
cumstances ; thus after taking carbonated drinks (champagne, 
seltzer water), in disturbances of the respiration where the 
supply of oxygen is diminished, after eating sugar in excessive 
amount, etc., although the special conditions under which this 
formation takes place are still undiscovered. 

According to O. Schultzen,^ human urine normally contains 
in twenty-four hours about 0*1 grm. of calcic oxalate. (Accord- 
ing to Neubauer it is sometimes quite free from it; see page 
168.) In a few cases of icterus, however, this amount increased 
fivefold. 

The question has been repeatedly raised how it happens 
that calcic oxalate, which is nearly insoluble in water, can j)ass 
through the walls of the vessels in the kidney and get into the 
urine. Some investigations by Neubauer t and ModdermanJ 
give information on these points, and show that calcic oxalate 
is somewhat soluble in the acid phosphate of sodium, and also 
that chloride of sodium, sulphate of sodium, chloride of potas- 
sium, etc., and even urea aid in its solution, though in slight 
degree. 

What importance, wdth reference to the diagnosis, prognosis, 
and treatment of disease does the presence of calcic oxalate in 
the urine afford? 

In this relation we must distinguish two classes of cases : 

1. If the urine for a long time continuously, weeks or even 
months, contains large quantities of calcic oxalate, there exists 
a so-called oxaluria, oxalic acid diathesis. This condition always 
demands the careful attention of the attending physician for 
two reasons. 

a. Because of the danger, under such circumstances, of calcic 
oxalate calculi, so-called mulberry calculi, being formed in the 
kidneys or bladder. 

b. And on account of the evil effects which oxalic acid may 
have on the system generally. It is known that oxalic acid 
taken internally in large amount exerts a poisonous action, not 

* Quantit. Bestimmung des oxals. Kalkes im Ham, Archiv f. Anat. uud 
Pliysiol., 1868, p. 719, et seq. 

f Arcliiv f. wissenschaft. Heilkunde, 1858, p. 1, et seq. 
X Sclimidt's Jalirb., Band 1S5, j). 145, etseq. 



URINARY SEDIMENTS, 421 

only locally on the portion of tlie intestine with which it comes 
in contact, but also generally on the heart and nervous system. 
From this circumstance it becomes probable, theoretically, that 
a large formation of oxalic acid within the body may also be 
productive of dangerous consequences. Many physicians, es- 
pecially in England and America (Prout, Begbie, Frick, and 
others), have observed and described such cases of oxaluria. 

As little attention has hitherto been paid to this form of 
oxaluria in Germany, it appears desirable to give here in out- 
line the very clear description of this disease as given by Beg- 
bie.^' He says : 

There is a numerous class of patients, mostly persons in the 
prime of life and belonging to the male sex, ordinarily of a 
sanguineous or melancholy temperament, unaccustomed to vig- 
orous exertion, usually belonging to the higher classes of so- 
ciety and accustomed to indulgence in the luxuries of life, 
especially of the table. They suffer from indigestion, from its 
mildest to its severest forms. Often no apparent disease is 
present, but only the discomfort which imperfect digestion and 
defective assimilation bring about — a feeling of weight and 
jDressure at the pit of the stomach, with flatulence and palpi- 
tation a feAv hours after meals. More serious symptoms, how- 
ever, frequently appear, which are not confined to the digestive 
apparatus, but exert a very profound influence on the nervous 
system and threaten the mind of the patient. Such patients 
are usually capricious, sensitive, and irritable, or dull, despon- 
dent, and melancholic ; they are frequently worried with a fear 
of some serious disease threatening them, as consumption or 
disease of the heart, and on this account are not rarely very 
deeply disturbed mentally. In milder cases we observe in these 
patients the anxious bearing and general appearance of one 
whose health is disturbed — the tongue is coated, the skin dry, 
and the pulse irritated ; in inveterate cases, a dirty, dingy coun- 
tenance, increasing emaciation, falling out of the hair, tendency 
to furuncles, carbuncles, psoriasis, and other cutaneous diseases ; 
dull, deep-seated pains in the back and loins, haemorrhage from 
the intestine and bladder, incontinence of urine, and impotency. 
The progress of this affection may be slow and varied : under 

* Loc, cit. 



422 SEMIOLOGY OF HUMAN UBINE. 

tlie influence of proper diet and appropriate treatment, com- 
bined witli pure country air, the disorder may be arrested, and, 
even by appropriate therapeutic treatment, entirely removed. 
If, however, it be neglected or badly treated, the affection will 
surely exj)ose its victim to all of the dangers and sufferings of 
a calculus in the kidney or bladder, or to the still worse conse- 
quences of a malignant organic disease. 

The source of this affection is to be sought in the accumula- 
tion of oxalic acid in the blood. This poison is separated from 
the blood by the kidneys, and its separation in the form of 
calcic oxalate gives us a means of recognizing the disease, and 
thus inducing a cure by tolerably simple and efficacious treat- 
ment. 

According to Begbie, this treatment is as follows : Long con- 
tinuance in a proper diet of meat, milk, mealy vegetables, with 
the exclusion of saccharine substances ; warm clothing and luke- 
warm baths ; as drugs, nitrate of potassium, hydrochloric acid 
in doses of twenty drops two or three times a day, or in the 
following formula: I^. Acidi muriatici diL, acidi nitrici dil., 
syrupi aurantii aa !ss, aqu?e !iss, of which one tesispoonful is 
to be taken in a wineglassful of water before meals. 

Beneke "^ describes the injurious influence of oxalic acid on 
the body even more forcibly. He believes that the phosphate 
of calcium is dissolved by it and removed from the body. The 
deficiency of phosphate of calcium which is thus brought about 
results in a diminution of the organic process of cell-formation. 

Distinct proof is as yet wanting, however, that the symptoms 
described above as belonging to the o^xalic diathesis really do 
depend on an accumulation of oxalic acid in the blood, and the 
assumption of an oxalic acid diathesis is, therefore, declared by 
many, as Lehmann, Gallois, and Smoler, to be quite improper. 
If, however, we recollect that oxalic acid undoubtedly possesses 
a distinct poisonous influence on the body when given in large 
doses, and that every observant physician with much practice has 
had opportunity to observe cases which quite correspond to the 
description given by Begbie (I have met with several such my- 
self), it would appear justifiable to advise practitioners not to 
neglect those cases in which large quantities of calcic oxalate 

*Loc. cit. 



UnmABT SEDIMENTS. 423 

appear for a long time continuously in the urine^ and, more- 
over, to investigate carefully its causes (disturbances of the 
respiration with diminished absorption of oxygen, immoderate 
eating of sugar, disturbances of any other intermediate meta- 
morphosis), and to carry out the treatment recommended above. 
2. On the other hand, it is certain that all of the cases in 
which calcic oxalate is observed in the urine do not come under 
the category described. Where only traces of this salt are found 
in the urine, or when large quantities of it appeax only tempo- 
rarily, as is often observed in the course of certain acute and 
chronic diseases, the danger spoken of above is not to be 
feared. The physician here has the task of investigating the 
cause of this occurrence : whether, perhaps, food or medicine 
containing oxalic acid gives rise to it ; or whether demonstra- 
ble changes in metamorphosis are the cause. In such cases 
the prognosis is not so bad, and we have only rarely to fear the 
bad results of oxalic acid described above. But it appears 
advisable here also, after we have obtained the causes of the 
abnormal condition, to combat it at once by proper treatment 
(especially substituting an animal diet for a largely vegetable 
one), and thereby obviate the possible evil consequences. 

§ 111. Cystin.^ 

The practical signification of cystin is of relatively small im- 
portance, since it seldom occurs in the urine. We only know 
at present that cystin sometimes gives rise to the formation of 
calculi. In such cases it always appears as a urinary sediment, 
and for this reason we mention it here, though cystin may also 
exist in solution in the urine. 

Whether the formation of this substance in the body is in 
any way injurious by producing alterations of the intermediate 
metamorphosis is not yet determined. It is not probable, how- 
ever, since, according to experience, cystin may be present in 
the urine for years Avithout disturbing the health when a cystin 
calculus is not formed. 



* A. Fabre, De la cystine, etc., Paris, 1859. Jul. Mtiller, Arcliivd. Pliarmacie, 
1852, p. 228, et seq. Toel, Annal. d. Chemie u. Pliarmacie, Band 96, p. 24, et 
seq. Bartels, Vircliow's ArcMv, 1863, p. 419, et seq. 



424 SEMIOLOGY OF EU3fAN URINE. 

For the detection of this body in the urine by chemical and 
microscopic examination, see § 47. 

The causes which give rise to its formation in the body are 
still quite unknown. The large amount of sulphur which it 
contains (more than 26 per cent.) indicates its relation to taurin, 
and we are, therefore, led to presume that perhaps the liver 
plays a role in its formation. 

Indeed, Scherer has found cystin in the liver, a proof that this 
substance, like urea, uric acid, etc., is not formed in the kidneys 
but elsewhere in the body, that it is taken up by the blood and 
separated again from it by the kidneys. 

Marowky * observed a case in which the presence of cystin 
in the urine was combined with almost complete chronic acholia, 
and supposes that a vicarious elimination of the taurin, which 
contains sulphur, took place by the kidneys in the form of cystin. 

Future investigations, let us hope, will yield information as 
to the significance of the appearance of cystin in the urine, and 
the more intimate conditions of its formation. 

It is an interesting fact that in the tolerably rare cases in 
which cystin has been found in urinary calculi and sediments, it 
has been present in a large ]3roportion of the cases in several 
members of the same family. 

Two cases which I had the opportunity of observing a short 
time ago, through the kindness of Dr. H. Harnier of Wildungen, 
confirm this. They were two brothers, young Hollanders, born 
in the East Indies, both of whom, otherwise well, suffered from 
cystinuria, which at times increased to the formation of gravel 
and small calculi. 



§ 112. XaNTHIN. HyPOXANTHIN. TYKOSIN.f 

Xanthin (see § 5 and § 49), formerly found only in very rare 
cases as a constituent of human calculi, afterward found in very 
small quantity in human urine, etc., has recently been observed 
also as a crystalline urinary sediment.:]: The significance of such 

'^ Deutsclies Arcliiv f . klin. Med. , iv. , p. 449, et seq. 

f Strecker, Anna!, d. Cliemie u. Pliarm., Band 102, p. 108. Stadeler, Ibid., 
Band 111, p. 28. Sclierer, Ibid., Band 112, p. 257. Jaillard, Calcui de xanthine, 
Alger, medic, 1873, Nr. 1, n. Centralbl. f. d. medic. Wissensch., 1873, No. 35. 

\ Bence Jones, Journ. of the Chem. Society, 1862, p. 68, et seq. 



URINARY SEDIMENTS. 425 

a sediment for the practitioner depends only on its liability to 
cause the formation of urinary calculi. The causes which give 
rise to an increased formation of xanthin in the body and to its 
existence as a sediment are as yet unknown. 

Hypoxanthin (sarkin) is a body closely allied to xanthin ; it 
occurs in small quantity in different organs of the human body 
(spleen, liver, pancreas), and probably, also, sometimes in the 
urine. (Strecker.) It must undoubtedly be regarded as a pro- 
duct of animal metamorphosis, and in its chemical constitution 
it is very closely allied to uric acid. (Compare page 33.) Still, 
we know so little concerning its origin and signification at 
present, that it seems sufficient to merely mention it here. 

Hosier ^ lays stress on the appearance of hypoxanthin in the 
urine as a characteristic symptom of splenic leukaemia. Sal- 
kowskyt was unable to confirm its occurrence, and the same 
may be said of E. Eeichardt.J 

Tyrosin (see § 37 and § 48), is a substance which results from 
the decomposition of the protein substances. It has been ob- 
served in different organs of the human body, usually associated 
wdth leucin, and in rare cases it occurs as a urinary sediment. 
"When it appears in considerable quantity in the urine it indi- 
cates alterations of the metamorphosis (excessive decomposi- 
tion of the protein substances), and thus is of interest to the 
physician. It has thus far been found in the urine, especially 
in acute atrophy of the liver, and is to a certain degree charac- 
teristic of this disease. It was also present in a few cases of 
leukaemia, typhoid fever, small-pox, etc. (Compare also § 133.) 



B. Organized Sediraents. 

Mucus AND Epithelium. 

§113. 

Urinary sediments consisting of mucus and epithelium are 
quite imj^ortant to the practitioner, and as they usually appear 
together, we will consider them together here. 

•^ Vircliow's Arcliiv, 37, p. 43, et seq. 

f Vircliow's Archiv, 1870, 50, p. 174, et seq. 

I Jena'sche Zeitsclirift, v., p. 389, et seq. 



426 SEMIOLOGY OF HUMAN URINE. 

All urine, even of healthy people, contains a little mncus, 
which is derived from the mucous membrane of the urinary 
passages, particularly of the bladder and urethra. In women, 
not unfrequently, mucus and epithelium from the vagina are 
mixed with the urine. The presence of a small amount of mu- 
cus in the urine, therefore, has no pathological importance. It 
usually appears in the form of a light cloud, which very gradu- 
ally sinks to the bottom, and is best recognized when the urine 
is observed in a glass by transmitted light. 

"When there is an abnormal increase in the amount of mucus 
this cloud increases, and a slimy sediment appears when the 
urine is left at rest for a time. With a little practice we can 
determine approximately by observation the quantity of mucus, 
and, moreover, this method of its estimation not only accom- 
plishes our object more quickly, but, as a rule, gives better re- 
sults even than the very complicated chemical processes which 
are not easily employed by the j)hysician. 

For the detection of mucus see § 50. Pure mucus is recog- 
nized under the microscope only with difficulty or not at all, 
since it forms a perfectly transparent mass which does not 
catch the eye. Epithelial cells, found mixed with it, are very 
distinctly recognized, however, from their characteristic ap- 
pearances. If the mucus is precijDitated by alcohol, or acids, 
however, it is recognized very readily as an indistinctly fibril- 
lated mass. It is rendered more distinct by the addition of 
diluted tincture of iodine, which not only precipitates, but 
colors it. 

If such a specimen of urine is filtered, the mucus remains as 
a tenacious mass on the filter, and, after drying, has a varnish- 
like appearance. A small quantity of mucus may remain in 
solution in the urine even after filtering, and this gives the 
chemical characteristics of mucin, described on page 175. 

The microscope shows us that the slimy urinary sediment 
frequently includes, in addition to the epithelium, other foreign 
matters : spermatozoa, crystals of calcic oxalate, urates, ammo- 
nio-magnesian phosphate, etc. ; therefore, in all cases in which 
an accurate diagnosis is required, this supposed mucus must 
be carefully examined with the microscope. 

An increased quantity of mucus in the urine indicates to the 
physician that there is an irritation of the mucous membrane 



UHmABY SEDIMENTS. 427 

(blenorrhoea) in some part of the uropoetic system — or in 
women, of the genital mucous membrane. This blenorrhoea 
may form a purely local 2:>rocess, or it may be the result of a 
general disease. For the latter reason the quantity of mucus 
and epithelium appears to be increased in the urine not unfre- 
quently in various febrile diseases — typhoid fever, pneumonia, 
etc. 

In a circumscribed blenorrhoea of the urinary passages, the 
situation of the affection may sometimes be recognized by the 
shape of the epithelial cells. 

The desquamated epithelium of the urinary tubules almost 
always forms large cylindrical bodies having the diameter 
and shape of the urinary tubules (epithelial casts). (Compare 
§ 116, 1.) _ 

The epithelium of the rest of the urinary passages from the 
pelvis of the kidney to the urethra is of the pavement variety, 
arranged in several layers. The most superficial layer consists 
of more or less flat cells, which in the pelvis of the kidney 
appear on the whole smaller, less flattened, sometimes irregu- 
lar and furnished with projections ; while in the bladder they 
are usually larger and more flattened, and sometimes present 
grooved depressions on their posterior surface which is turned 
toward the middle layer. The middle layer consists especially 
of smaller, more oval and club-shaped caudate cells. The 
deepest layer of cells consists of still smaller round cells, so- 
called mucous corpuscles. 

If we bear in mind these relations, we may frequently be 
enabled to determine whether the desquamated epithelium 
contained in the urine came from the urinary tubules or from a 
lower portion of the urinary passages ; and, in the latter case, 
whether it belonged to the superficial or deep layers, and 
whether it came from the pelvis of the kidney or the bladder. 

When there is a very great increase in the quantity of mucus 
in the urine, there is almost always a tendency to the acid 
or alkaline fermentation, which the practitioner must carefully 
take into consideration on account of the attendant results — in- 
creased irritation of the mucous membrane of the urinary ]pas- 
sages and formation of urinary concretions. 

Further, we may observe that pus corpuscles in ammoniacal 
urine may be converted into a jelly, which bears the greatest 



428 SEMIOLOGY OF HUMAN UBmE. 

resemblance to mucus, so that the physician frequently sup- 
poses he has a mucous urinary sediment before him, when in 
reality it does not consist of mucus, but of pus corpuscles 
which have been transformed into a gelatinous mass. (See the 
following section.) 

§ 114. Pus. 

Recognition. The microscope is always required to distinguish 
pus in the urine with certainty. With it pus corpuscles are 
recognized by their shape and size, as well as by the very char- 
acteristic nuclei which are made clear by the addition of acetic 
acid. (See § 52.) The abnormal pus corpuscles described below 
form the only exception to this. A discrimination between pus 
corpuscles and so-called mucous corpuscles is neither possible 
nor of practical importance, since the two kinds of corpuscles 
are quite identical. 

Large quantities of pus in the urine always form a sediment. 

If only a few pus corpuscles are present in the urine, a visi- 
ble sediment is a long while in forming. To discover the pus 
corpuscles in this case the urine must either be allowed to 
stand for several hours in a tall glass and then the lowest layer 
be examined microscopically, or we must filter it and place 
that which remains on the filter under the microscope for ex- 
amination. 

There are cases, however, in which pus cannot be detected 
in the urine with certainty, but can only be inferred. This 
happens wdien the urine containing the pus is strongly am- 
moniacal. The pus corpuscles are changed into a ropy gela- 
tinous mass by the carbonate of ammonium present, and their 
shape and outline is destroyed. Such a mass is generally taken 
for mucus and the process causing it regarded as a blenor- 
rhoea, when in fact it is a pyorrhoea, and the presumed mucus 
is merely pus, whose corpuscles have been destroyed by the 
influence of the alkali. 

Since in every suppuration in addition to the pus corpuscles 
there is also present a pus serum which contains albumen, 
it is evident that all urine containing pus also contains a 
little albumen, which may be demonstrated by the usual tests ; 
naturally when the urine is alkaline the necessary precautions 
must be taken. (Compare § 97.) 



UBINART SEDIMENTS. 429 

Importance. Pus in the urine always indicates a suppurative 
process in the uropoetic system or an abscess communicating 
with it. Only in women is it possible that pus in the urine 
may be derived from the genital organs, the vagina, or the 
uterus. 

Pus in the urine may be derived from the different parts of 
the uropoetic system : from the urethra in gonorrhoea, from 
the bladder, the ureters, the pelves of the kidneys, and even 
from the parenchyma of the kidney in suppuration of that or- 
gan. It may spring from several of these parts of the uropoetic 
system at the same time. The accurate determination of the 
true source of pus does not always appear to be easy. The 
following points, however, may prove of some service in the 
diagnosis : 

In blenorrhoea of the urethra a purulent fluid may be pressed 
out of the urethra between the micturitions. The secretion 
then appears usually in the form of shreds in the urine. 

If the pus come from the bladder symptoms of acute or 
chronic disease of the bladder are always present (strangury, 
etc.). 

Suppuration in one or both ureters is accompanied by slight 
colicky pains along the course of the ureter. 

Suppuration confined to the parenchma of the kidney is 
sometimes accompanied by so slight local symptoms, that it is 
only discovered accidentally by the continued presence of pus 
in the urine. 

Example. K., a man thirty-six years of age, entered the Gies- 
sen clinic on account of a rheumatic-gastric fever. He re- 
covered rapidly, and was about to be discharged, when the 
sudden occurrence of a tolerably abundant sediment of pus 
corpuscles in his urine occasioned his retention in the hospital 
for a short time longer for observation. This sediment con- 
tinued for weeks, the patient not having the slightest difficulty 
of micturition, indeed no symptom which pointed to disease of 
the uropoetic system. Subsequently pain was felt in the region 
of one kidney and frequent chills occurred. An intercurrent 
typhoid fever, which was then epidemic, unexpectedly put an 
end to the patient's life, and the autopsy showed an almost 
complete suppuration of the parenchyma of one kidney withoiit 
any further disease in the urinary apparatus. 



430 SEMIOLOGY OF HUMAN UBINE. 

It is of great practical importance in such, cases to determine 
wlietlier the pus is the product of a superficial affection of the 
mucous membrane (catarrhal inflammation), or whether it is the 
result of a more profound and extensive alteration of the parts. 
The following facts will assist in deciding this question : 

The duration of the suppuration. The temporary presence 
of pus in the urine, lasting only a few days, always allows us to 
conclude that there is merely a superficial affection. 

The cliarader of the pus as seen on microscopic examination. 
Perfectly normal pus corpuscles of quite round shape present- 
ing on treatment with acetic acid the characteristic double or 
triple nuclei indicate laudable pus and a simple catarrh of the 
mucous membrane. Abnormal pus corpuscles, on the other 
hand, with irregular forms and contours, and which present ir- 
regular nuclei on treating with acetic acid, or an ill-defined, 
finely granular mass mixed with irregularly shaped pus corpus- 
cles and partially destroyed cells, indicate the probable exist- 
ence of a deep-seated suppuration, ulceration, or tuberculosis. 
(Compare the following section.) 

Various substances were formerly included under the head 
of pus in the widest sense of the word, which could not be dis- 
tinguished by the unaided eye, and which the microscope alone 
has now allowed us to distinguish. The recognition of these 
substances has a great practical significance. Of this class are 
cancerous and tuberculous masses and urinary casts. 

§ 115. Cancerous and Tuberculous Masses. 

Cancerous and tuberculous masses sometimes occur as uri- 
nary sediment, and are important in indicating to the physician 
the fact that softening has occurred in cancerous or tubercu- 
lous deposits in some portion of the urinary organs. 

Masses of cancer occur in the urine most frequently as the 
result of cancer of the bladder, more rarely of cancer of the 
kidney. The cancer is generally of the soft variety, encepha- 
loid, and, as a rule, appears in the urine in the form of small 
masses, aggregations of cells — mother and daughter cells — with 
thick walls or caudate and long spindle-shaped cells. In such 
cases the urine also usually contains blood and blood coagula. 

Distinct symptoms of disease of the bladder are always pres- 



TJRmARY SEDIMENTS. 431 

ent in cancer of that organ : difficulty of micturition, frequently 
also symptoms which point to a simultaneous disease of the 
rectum, or in women of the vagina, so that the diagnosis usually 
presents no difficulties. 

Cancer of the bladder is generally a so-called villous cancer, 
that is, it is made up of compound branched villi, which are 
sometimes hollow and consist of a fibrous stroma covered with 
a layer of variously shaped epithelial cells ; sometimes also it 
consists of an amorphous base with cells imbedded in it. The 
detached portions of this cancer of the bladder, which occur as 
a sediment in the urine of those patients in whom the can- 
cer has softened and separated, are, therefore, of very various 
shapes, but at the same time they are very characteristic and 
are of essential service in enabling us to diagnosticate such a 
disease with certainty. 

Fig. 5 and 6 in Plate III. represent a few of the most charac- 
teristic forms of such cancers as they appear in the urinary 
sediment. They are in part taken from the valuable work of 
Dr. Lambl,^ and partly from my own observations. Fig. 5, A, 
represents a large fragment of villous cancer of the bladder, 
very branched, as it appears with a low magnifying power (from 
20 to 50 diameters). 

B represents the terminal portion of a villous cancer more 
highly magnified (about 200 diameters). The inner part con- 
sists of an amorphous fibrous stroma containing numerous oval 
nuclei and externally covered with a compound layer of epithelial 
cells. 

C represents isolated cells from the epithelial layer of such 
a cancer. They are mostly irregular in form, partly caudate 
and branched, quite large, and containing a large nucleus. 

D is a villous cancer of a somewhat different character. Tol- 
erably large nuclei are enclosed in an amorphous mass which 
forms warty excrescences. The epithelial layer is wanting. 

Fig. 6, A. Fragment of a villous cancer consisting of a fibrous 
(hollow?) cylinder, which is covered with epithelium (in the 
figure stripped off in places) in the form of small nucleated 
cells. 

" Ueber Harnblasenkrebs. Ein Beitrag zur mikroskopischen Diagnostik am 
Krankenbette mit vier Tafeln. » Prager Vierteljalirsclir., 1856, Band 49, p. 1, 
et seq. 



432 SEMIOLOGY OF HUMAN URINE. 

B is a mass of large cancer-cells with large cell-cavities, thick 
cell-wall and nuclei ; the latter in some cases is enclosed in the 
cell-Avall (B, c). The cells are partly united by means of an 
amorphous connective substance into large groups (B, a), and 
they are in part isolated (B, b, and B, c). 

C. Fragment of an amorphous, fibrous cancer stroma having 
spindle-shaped nuclei and elastic fibres, on which larger cells 
rest — the remains of the epithelial covering — in part well pre- 
served (aa), in part half destroyed (b). 

D. Isolated cells probably derived from the epithelial cover- 
ing of a villous cancer of the bladder ; aa, small round cells 
with nucleoli (or nuclei?) distinctly colored red, and at first 
sight resembling blood corpuscles ; in large masses forming a 
urinary sediment resembling blood, but not afi'ected by acetic 
acid ; bb, large, irregular, partly caudate cells, having reddish 
nuclei containing nucleoli. They are found mixed with the 
small cells (nuclei?), aa. (Comj)are § 134, case 13.) 

Cancer of the kidney, on the other hand, is usually much 
more difficult to diagnosticate. Sometimes when cancer-cells 
are present in the urine, we can determine the existence of the 
disease by negative signs, as all symptoms pointing to a disease 
of the bladder are wanting ; sometimes also we can determine it 
by percussion through an enlargement of one or both kidneys. 

Masses of tubercle in the urine resemble pus when seen 
with the unaided eye, but they may be distinguished from it 
by their microscopic appearance. They consist of irregular 
pus corpuscles in addition to an ill-defined detritus — fragments 
of cells, necrosed connective tissue and elastic fibres, imj)erfect 
nuclei, and an indistinct, finely granular mass with which frag- 
ments of cholesterin crystals are sometimes mingled. The seat 
of the tubercular deposit which gives rise to urinary sediments 
of softened masses of tubercle is the mucous membrane or the 
submucous tissue ; it may take j)lace in the bladder, the ure- 
ters, or the calices of the kidney. In affections of this kind, 
which have lasted a long time, the tubercular deposit, as a rule, 
extends over a great portion of the mucous membrane of the 
urinary tract, from the kidneys even to the bladder. 

The following histories of patients may serve to give infor- 
mation concerning the diagnosis of tubercular deposits in the 
uropoetic system : 



URmART SEDIMENTS. 433 

1. A young man, twenty-five years old, souglit aid at my 
clinic for an affection of tlie bladder which had troubled him 
for a year. Micturition was difficult and painful, the urine was 
sometimes bloody, and deposited a sediment on standing, which 
contained blood and pus corpuscles partly normal and partly 
abnormal. (The latter were not perfectly round, but w^ere 
angular and knobbed ; when treated with acetic acid, they did 
not show normal nuclei, but were either wholly without nuclei 
or showed only small irregular nucleoli.) Besides this the sedi- 
ment contained an irregular, granular, amorphous mass, in part 
finely divided, in part combined into larger masses up to the size 
of the head of a pin. A careful examination, moreover, showed 
that the prostate was enlarged, very sensitive on pressure, and 
that there was an advanced tuberculosis of the lungs. The 
patient had never suffered from gonorrhoea or chancre. A diag- 
nosis of tuberculosis of the bladder and ]3rostate was made, and 
on the death of the patient a short time after from increase of 
the lung trouble, the diagnosis was confirmed by the autopsy. 

2. A man thirty years old, who had always been healthy, was 
seized with occasional attacks of pain, which passed from the 
region of the left kidney down to the bladder and terminated 
in very urgent and frequent calls to micturate. These par- 
oxysms lasted several hours, and were repeated again after in- 
tervals of complete intermission which sometimes covered a 
few days only, and sometimes lasted for several weeks. Half a 
year later a swelling formed in the left testicle, this broke and 
led to the formation of a fistula which obstinately resisted all 
attempts to heal it. The urine never contained gravel or con- 
cretions, such as would lead to the suspicion of calculus of the 
kidney, but after every attack it deposited a slight sediment 
consisting of pus cells, which, as in the former case, were very 
irregular, and when treated with acetic acid presented no nor- 
mal nuclei. Here, also, there was found in addition an ill-de- 
fined amorphous granular mass of the same appearance as that 
presented by tubercle-detritus under the microscope. This 
circumstance, together with the accompanying disease of the 
testicle, admitted of the diagnosis of tubercular deposit in the 
left ureter. * 



* Compare also Kussmaul, Wiirzburger med. Zeitschr., 1863, p. 24, et seq. 
2S 



434 SEMIOLOGY OF HUMAN URINE. 

§ 116. Ueinaky Cylinders. Eenal Casts.* 

Urinary sediment, consisting of renal casts and cylinders, is 
of great practical importance in giving us information which 
will enable us to form a diagnosis and an opinion concerning 
certain diseases of the parenchyma of the kidney. This sedi- 
ment can be recognized with certainty only by a microscopic 
examination. Its forms and characteristics have been already 
described in § 53 ; we must return to this subject again, how- 
ever, in order to explain its importance under certain circum- 
stances. 

This sediment consists of long tubular or cylindrical bodies, 
which are formed in the urinary tubuli of the kidneys, espe- 
cially the tubes of Bellini in the medullary portion, and which 
take the form of these tubules more or less, and to a certain ex- 
tent form casts of them. The chief forms under which the ele- 
ments of this sediment appear are as follows : 

1. Einthelial Casts: Tubular masses of epithelial cells like 
those obtained by scraping with a knife a section of a fresh 
kidney through the medullary portion, and examining the fluid 
obtained microscopically. (See Plate I., fig. 4) The epithelium 
of the tubules of Bellini is thrown off in coherent masses by a 
pathological process and is evacuated with the urine. Besides 
these larger epithelial tubules, single epithelial cylinders (cau- 
date cells) are frequently found which are derived from the 
calices or the pelvis of the kidney (Plate I., ^g. 4) ; sometimes 
also pus corpuscles are present. 

2. Granular Renal Casts (Plate I., fig. 6). These are solid cy- 
linders, resembling those just described in form and size, but of 
a finely granular appearance. Sometimes they enclose single 
epithelial cells, more frequently blood corpuscles, pus corpus- 
cles, as well as different kinds of crystals met with in urinary 
sediments, especially calcic oxalate. Blood corpuscles, pus cor- 
puscles, or granule cells are very often found mixed with them 
in the sediment. 

•^L. Rovida, Ueber das Wcsen der Harncylinder in Molescliott's Unters. zur 
Naturlelire, xl., p. 1, et seq. A. Burkart, Die Harncylinder, Gekronte Preis- 
sclirift, Berlin, Hirscliwald, 1874. H. Senator, Ueber die im. Harne vorkom- 
menden EiweisskcJrper, etc., iiber Harncylinder und Fibrinausscliwitzung, Vir- 
chow's Arcbiv, 1874, Ix., p. 466, et seq. 



UBINABY SEDIMENTS. 435 

3. Hyaline Benal Casts (Plate I., fig. 5). These are also solid 
cylinders, like the last, but they are so pale and transparent that 
it is very difficult to distinguish them under the microscope 
from the surrounding fluid. They are rendered more distinct 
by adding to the urine a little solution of iodine in iodide of 
potassium or in glycerine, which gives them a brownish color. 

There are many transitions between the forms 2 and 3 ; the 
hyaline casts, for example, take up pus corpuscles here and 
there, or granular molecules or fat drops and fat granules, and 
thus resemble the granular form. 

Moreover, we should observe the diameter of these casts. 
Sometimes the diameter is small, -^^-^ of a line ; in other cases 
it is larger and may reach -f^ of a line or more. Sometimes the 
casts are of unequal diameter, they are small at one point and 
broader at another, varicose or flask-shaped. 

Since casts and cylinders in many cases occur only in small 
numbers in the urine, to ascertain with certainty whether any 
are present or not, we must either allow the urine to stand a 
long time and examine the sediment microscopically, or what is 
still better, we must filter it and place the magma which re- 
mains on the filter under the microscope, as this will contain all 
of the casts and cylinders. It is a good plan to color the urine 
by adding a solution of iodine in iodide of potassium, so as not 
to overlook any of the transparent hyaline cylinders, which are 
so difficult to see. Sometimes forms are met with in the urinary 
sediment which somewhat resemble granular casts, and which 
may be erroneously mistaken for them. Such are cylindrical, 
sausage-shaped bodies which consist of masses of fine mole- 
cules. (Plate II., fig. 2.) They are found chiefly in albuminous 
urine, or in urine which has stood a long time and has already 
undergone partial decomposition. They result from a finely 
granular precipitation of albumen, mucus and the like. The 
skilled observer readily distinguishes them from true granular 
casts by their less regular shape. 

Imjjortance. Eenal casts and cylinders always spring from 
the urinary tubules of the kidneys, especially from the tubules 
of Bellini in the medullary portion, and they indicate disease 
of these tubules. They are usually regarded as a sure sign of 
so-called Bright's disease. Since, however, the name " morbus 
Brightii " is at most only a somewhat indefinite collective term, 



436 SEMIOLOGY OF HUMAN URINE. 

under which all varieties of disease of the renal parenchyma 
are usually included, it is insufficient for a careful diagnosis, 
prognosis, and treatment. We will attempt in the following 
pages to ascertain a little more accurately the indications of the 
different forms of these products. 

Upithelial casts in the urine indicate that a separation of the 
epithelium of the tubules of Bellini (desquamative nephritis) 
is taking place. This process may be temporary Avithout leav- 
ing any further consequences behind. Therefore a urinary 
sediment which consists merely of epithelial casts and which 
disappears again in a few days allows of a favorable prognosis. 
If pus corpuscles are found mingled with the epithelial casts, 
this points to a more severe imflammatory process (pyorrhoea) 
either in the parenchyma of the kidney or in the calices and 
pelves of the kidneys. 

Granular and hyaline casts, on the other hand, always indicate 
a graver disease of the jDarenchyma of the kidney, which gene- 
rally assumes a chronic course. The hyaline casts probably arise 
from an exudation of a fibrinous fluid into the renal canals with 
subsequent coagulation of the fibrine (croupous inflammation). 
The granular casts are formed either by a further metamorpho- 
sis of the exudation in the urinary tubules or by a degeneration 
of the glandular epithelium lining the tubules. 

According to Eovida the colorless renal casts do not consist 
of fibrine and are also different from other kinds of albumen. 
Senator also does not consider the albuminous renal casts of 
all diffuse diseases of the kidneys as blood or exudation fibrine, 
but as products of the disturbance of nutrition of the glandular 
epithelium. 

The larger the quantity of casts in the urine and the longer 
time they are present, the more extensive is the degeneration 
of the kidney apt to be, and as a rule, therefore, the more un- 
favorable is the prognosis. 

If there is quite an amount of fat in the casts, and if it lasts 
a long time (recognizable as fat drops and granules imbedded 
in the casts), we may infer that the degeneration of the kidneys 
inclines to a fatty one. 

When blood continues to be present in the casts, or in the 
urine containing casts, we may conclude that there is especially 
a disease of the vessels of the kidney — rigidity, fatty or amy- 



UBINARY SEDIMENTS. 437 

loicl degeneration of tlie renal arteries, especially of tlie vascu- 
lar coils, Avhicli, as Malpighian bodies, project into the origins 
of the renal tubules. 

Casts of very small diameter indicate a probable contraction 
and narrowing of the renal tubules, and unusually large ones 
indicate a dilatation of the renal tubules. Casts of very un- 
equal diameter, with bulgings and contractions, allow of the 
conclusion that there is a varicose or distended condition of 
the renal tubules. 

When, as often happens, several of the modifications men- 
tioned occur together, we have reason to assume that the 
pathologico-anatomical changes in the kidney are very compli- 
cated. 



Blood corpuscles occur not infrequently as a urinary sediment. 
(Compare § 51 and § 99). We have already spoken of tlieir 
significance to the physician in § 99. If they are in moderate 
quantity, together with renal casts and pus corpuscles, we may 
conclude that we are dealing with a case of a commencing or 
an advanced nephritis parenchymatosa or Bright's disease. 

In rare cases granules or flakes of blackish-brown pigment 
are found in the urinary sediment. S. von Basch ^' describes 
them as pale flocculi thickly filled with dark brownish, finely 
granular pigment, some of which have the shape and size of 
cells, while the most of them are much larger and are of irregu- 
lar shape. They indicate a plugging and rupture of the renal 
vessels produced by the melauEemia.t (See page 394) 

§ 117. Ikfusoeia. Fungi — (Kyesteine).:]: 

Fungi and infusoria rarely exist in fresh normal urine ; they 
must, therefore, gain access to it accidentally through unclean 
vessels, etc. They occur frequently, however, in urine which 

'" A case of melansemia. Wiener medic. Jalirb., 1873, ii. 

f Further details may be found in J. Vogel's Krankheiten dcr liarnbereiten- 
den Organe, in R. Vircbow's Handbneb der Patbologie und Tberapie, Band vi., 
p. 600. 

XA. Hill Hassall on tbe development and signification of Vibrio lineola, Bodo 
urinarius, and on other fungoid products, etc., in urine. Lancet, Nov. 1859, 
ii. 31. 



438 SEMIOLOGY OF HUMAN UBmE, 

has been kept a long time, and are almost always present in 
urine which has undergone decomposition. 

L. Pasteur"^' rightly calls attention to the fact that the germs 
of these fungi and infusoria always get into the urine from 
without, and are not formed in it by the so-called generatio 
sequivoca; moreover, it is usually after the urine has been 
passed that the fungi and infusoria appear, and they are the 
true cause of the acid and alkaline fermentations as well as of 
the decomposition of the urine. Urine from wliich these germs 
have been carefully excluded may be kept without decompos- 
ing. Since they are in any case the chief cause of a putrid 
decom230sition of the urine with all of its results, such as de- 
composition of the urea, precipitation of many of the urinary 
constituents, irritation of the mucous membrane of the urinary 
passages, etc., we must take heed that such germs do not gain 
access to the urinary passages by the passage of unclean cathe- 
ters, etc., and by rapidly increasing there bring about the evil 
consequences mentioned. 

The infusoria are almost always very small, and are recog- 
nized under the microscope, when quite high powers are used, 
by their motion. They consist either of punctiform monads 
or of rod-like vibriones and bacteria. Karely they are larger, 
roundish, resemble mucous cells and have thread-like apj^en- 
dages (Bodo urinarius — Hassall). They are found chiefly in 
putrid urine which contains albumen, mucus, blood, or pus, 
and are practically important, since they may favor or even set 
up putrid decomposition of such a specimen of urine. If they 
have formed already within the urinary passages, their germs 
have probably always obtained entrance from without, fre- 
quently in the manner described, by the introduction of un- 
clean catheters. In all such cases, however, we must satisfy 
ourselves that the vibriones have not come from accidental 
mixture of putrid matters with the urine after its passage, from 
unclean vessels, or similar sources. 

Fungi usually appear in the urine in the form of roundish or 
oval cells (spores and sporules), which are sometimes united in 
rows like a rosary (torula form) — less frequently they appear 
in the form of simple, compound or branched threads (thallus, 

* Comptes rendus, 1860, i., p. 841. 



UBINARY SEDIMEN'TS. 439 

mycelium). These latter usually do not occur until after tlie 
urine has been kept a long time, and, therefore, they are not of 
much practical importance. Of these fungi which occur in 
urine, those which are of chief interest to the physician are : 

1. The torula-like fungus observed by Yon Tieghem and de- 
scribed on page 188, on which the alkaline fermentation of 
urine is said to depend. The conditions of its origin and de- 
velopment, however, require a more accurate investigation. 

2. Yeast spores (Hormiscium sacchari), which occur only in 
saccharine urines, and may, therefore, be utilized for the detec- 
tion of glycosuria. They are also roundish or oval cells, which 
sometimes enclose a nucleus ; they are, however, somewhat 
larger than the preceding (0*004 to 0*007 mm. in diameter). 
They increase by budding to torula-like rows, which are com- 
posed of from two to four cells. (See Plate II., fig. 2, and page 
189, fig. 5.) 

3. Sarcince (vide page 189, fig. 6). It appears to have quite 
as little real specific significance in the urine as it has in other 
cavities of the body (stomach and intestines, lungs), where it 
appears more frequently ; it is probably, therefore, to be re- 
garded as an accidental parasite. The presence of sarcinae in 
the bladder probably favors the decomposition of the urine, 
produces alkalinity, a deposition of the earthy phosphates, etc., 
and therefore it has a practical interest.* 

Other fungi which are occasionally observed in urine which 
has been kept a long time belong to the most common forms, as 
penicilium, etc., whose spores are very widely disseminated, 
and may develop in the urine under favorable conditions when 
they have gained access to it. They are, therefore, without 
significance to the physician. 

Under this head belongs the so-called Kyesteine which was 
thought to be present only in the urine of pregnant women ; 
and therefore that it could be utilized as a means of diagnosti- 
cating pregnancy. This name was applied to a pellicle which 
forms on the surface of urine after it had stood for a long time, 
usually several days. Microscopic examination of it shows, 
however, that it consists of very various elements, for the most 

* Besides tlie literature already mentioned, see also Sarcinae in the Urine (F. 
Bateman, Lancet, 1867, i., No. 6). 



440 SEMIOLOGY OF HU3IAN URINE. 

part of a largo mass of vibriones with fungi, of crystals of am- 
monio-magnesian phosphate, small drops of fat, etc.; it is, there- 
fore, no simple substance which requires a special name. More- 
over, this pellicle does not occur exclusively in the urine of 
pregnant women, but is also found frequently in that of women 
not pregnant, and even in that of men, so that it has no diag- 
nostic value for pregnancy. 

§ 118. Spermatozoa. 

Spermatozoa can be detected in the urine only by the aid of 
quite high powers of the microscope. They are readily recog- 
nized by their peculiar tadpole shape. Since they rarely occur 
in large numbers, often only a single one being found in the 
urine, it is necessary to allow the urine to stand at rest in a coni- 
cal glass (champagne glass) for a long time in order to find them 
with certainty ; this is accomplished by carefully pouring off 
the upper part of the urine, and then examining microscopically 
the lowest part which contains the spermatozoa. 

Their importance is self-evident. In the urine of men they 
always indicate that a discharge of semen has taken place either 
from coitus or masturbation ; sometimes they lead to the detec- 
tion of onanism. In the urine of women they prove that coitus 
has taken place, provided that there has been no admixture of 
semen, intentional or otherwise, with the urine. 

The immature spermatozoa sometimes found by Clemens in 
the urine ^' indicates to the j)hysician that an unusually power- 
ful or an immoderately long-continued irritation of the genital 
apparatus has occurred, whereby not only mature but also im- 
mature spermatozoa have been ejected (onanism, excessive coi- 
tus, etc.). 



In rare cases entozoa also occur as a urinary sediment, when 
they have gained access to the kidneys or some other part of 
the urinary passages, and are passed with the urine. 

Of these the most frequent in Europe are : Eccliinococcus 
cysts, usually numerous, of the size of a pea, hazel-nut, walnut, 

* Henle and Pfeuffer's Zeitschrift, 1846, v., p. 133, and Deutsche Klinik, 1860, 
30. See also page 187. 



URINART SEDIMEWTS. 441 

and larger, formed of a structureless membrane and filled with 
serous fluid. Sometimes when these bladders are not sterile, 
the characteristic ecchinococcus heads and hooks may be seen 
with the microscope. Most of the ecchinococci which pass off 
with the urine are located in the kidney, though ecchinococci 
may also be situated elsewhere, in the pelvis, etc., make an 
opening into the urinary organs, and thus pass off with the urine. 

The following example will show how difficult it may some- 
times be to properly estimate such cases. A middle-aged man, 
otherwise well, suffered for years with a difficulty which oc- 
curred in paroxysms after longer or shorter intervals, and which 
indicated a disease of the urinary passages : there was occa- 
sional pain in the region of the left kidney, with albumen and 
pus, and sometimes also a moderate amount of blood in the 
urine. Various diagnoses were made by different physicians 
who were consulted, and corresponding courses of treatment 
were pursued (courses at Vichy, Karlsbad, etc.), but with no im- 
provement ; they, together with the ever-increasing fear that a 
serious renal disease existed which would shortly terminate 
fatally, rather reduced the patient. A careful examination of 
the urine passed during the attacks frequently showed the pres- 
ence of small membranous shreds, which were recognized by 
the microscope as fragments of a sterile ecchinococcus bladder. 
Since percussion gave only a moderate enlargement of the left 
kidney and the natural passage of the ecchinococcus bladders 
had commenced in a relatively favorable way, a not unfavorable 
prognosis was given. The patient, freed from his anxiety and 
under treatment which, besides mild diuretics, had as its chief 
object the avoidance of matters which could be injurious, re- 
covered in a comparatively short time.^ 

In Egypt the eggs of the Distomum hcematohium are found as 
a urinary sediment with tolerable frequency. They are oval, 
from 0'12 to 0*13 mm. long and from 0*04 to 0*05 mm. broad, and 
are characterized by a sharp point at one end, or by being 
armed with a pointed spine on the side.t 

* For f urtlier infonnation see J. Vogel, Kranklieiten der liarnbereitenden Or- 
gane, in Virchow's Pathologie und Therapie, Band 6, S. 691, ct seq. 

I For more particulars on this point and for tlie symptoms wliicli they cause, 
see Bilharz, Zeitschrift f. wissensch. Zool., iv., p. 59, 73, and 454. The same 
author, Wiener medic. Wochenschr. , 1856, Nr. 4 and 5. 



442 SEMIOLOGY OF HUMAN URINE, 

T. E. Lewis * found in the urine and blood of several persons 
suffering from cliyluria in Calcutta a peculiar entozoon (named 
Filaria immitis by Cobbold).t 

* Centralbl. f. d. med. Wissenschaf t. , 1873, No. 21 and 30. 

f For an account of a few other entozoa -wMcli are passed witli the urine in 
very rare cases, the reader is referred to our work on the Diseases of the Uri- 
nary Organs, in Virchow's Pathol, und Ther., Band 6, p. 555. 



DIVISION SECOND. 

QUANTITATIVE CHANGES IN THE URINE. 

§119. 

Much less attention lias been paid by the practitioner, until 
quite recently, to the quantitative changes of the urine, espe- 
cially the increase or diminution of the normal constituents, 
than to the qualitative changes of this fluid previously con- 
sidered. The reason of this was partly because generally less 
importance has been hitherto attached to the chemical element 
in disease and in the changes of metamorphosis, and partly 
because the methods formerly used in such investigations were 
very difficult, tedious, and lengthy, requiring much appara- 
tus, indeed frequently a complete laboratory, so that they 
were employed almost exclusively by chemists. By the re- 
cent introduction of new methods, however, especially the 
volumetric methods, many of the investigations of this sort 
have been greatly simplified, so that they may now be per- 
formed by the practitioner quite quickly, and without any large 
amount of apparatus. At the same time the importance, ne- 
cessity even, of the quantitative estimation of the various pro- 
cesses of metamorphosis in disease becomes evident; and it 
is to be hoped that in proportion as the importance of such 
investigations for purposes of diagnosis, prognosis, and treat- 
ment are brought out more distinctly, practitioners will avail 
themselves more frequently of them. I trust the following at- 
tempt to demonstrate the importance of such investigations to 
the practitioner, as far as it is possible at the present time, 
will assist somewhat in bringing them into more general use. 

The quantitative changes of the urine may be divided into 
two groups, according as they are more or less readily deter- 
mined. 

443 



444 SEMIOLOGY OF HUMAN UBINE. 

I. Those whicli may be discovered without an exact chemical 
analysis, and which, on account of their easy detection, are of 
especial value to physicians. 

II. Those which require a quantitative chemical analysis to 
detect them, and whose determination is, therefore, more diffi- 
cult and complicated. 

I. THE QUANTITATIVE ALTERATIONS OP THE URINE WHICH ARE 
EASILY DEMONSTRATED. 

Under this head belong : The quantity of the urine ; the solid 
residue, and the specific gravity of the urine ; and the color. 
The estimation of all of these is so easy, requires so little appa- 
ratus and so little time, that no practitioner is excusable for 
neglecting them in those cases in which they may contribute 
something to the more complete insight into a diseased pro- 
cess. 

§ 120. Quantity of Ueine.'^ 

The process proposed for estimating the quantity of urine 
has been already described in § 57. It is most easily deter- 
mined by measurement ; the determination by weight is more 
laborious. 

The estimation of the quantitj^ of the urine is only of value 
when we also know the time during which it was passed. It is 
best to collect the urine which has been passed either during 
twenty-four hours, or during every hour, or at least to calculate 
the quantity passed for this period. In accurate estimations of 
the quantity of urine it is absolutely necessary that the physi- 
cian should assure himself that all of the urine passed has been 
really collected, that none of it has been lost at stool or in any 
other way, and that no water, etc., has been poured into the 
urine vessel. 

A simple estimate of the quantity of urine, without weighing 
or measuring it, may sometimes give the physician important 
indications in certain cases, but it does not serve for accurate 
investigations. Since graduated urine-glasses can be easily 
and cheaply obtained at the present time, and since they are, 
moreover, much better adapted for displaying the color, trans- 



J. Vogel, ArcMv fiir gemeinschaftliclie Arbeiten, Band I., p. 104, et seq. 



QUANTITATIVE CHANGES IN THE URINE. 445 

parency, sediment, and other characteristics of urine, than por- 
celain or earthen vessels, the physician should give them the 
preference in all cases in private practice in which the examina- 
tion of the urine is important. 

In order to ascertain the average quantity of urine passed in 
chronic diseases (the quantity in an individual case), we must 
not be satisfied with measuring it for a single day ; for during 
that short period accidental influences may easily increase or 
diminish the quantity. The urine must rather be measured for 
several days in succession and the average be taken for twenty- 
four hours. 

To ascertain the influence of any temporary circumstances it 
is best to calculate the quantity of urine passed per hour. 

The determination of the quantity of the urine forms the basis 
of the quantitative estimation of all of its constituents. It is 
also in itself important oftentimes in showing the activity of the 
kidneys, and especially their power of separating water from the 
system. 

In many cases it is important to the physician to determine 
the relation of the quantity of urine to the amount of the pul- 
monary exhalation, perspiration, and fseces ; for many hints are 
thus obtained which may be of service in judging of the state 
of the disease, in giving a prognosis, and in recommending 
the treatment. Thus, in most chest, heart, and skin diseases a 
diminution of the urinary secretion, with an accompanying in- 
crease of the pulmonary exhalation, is an unfavorable sign, and 
the duty of the physician in such cases is to increase the uri- 
nary secretion, in order to relieve the diseased organs. Con- 
versely in most diseases of the kidneys, at least in their com- 
mencement, our object is to lessen the activity of the kidneys 
and diminish the quantity of urine by stimulating the other 
secretions. 

When the urine is permanently much increased (polyuria, 
diabetes), the determination of its quantity is the first and most 
important means of ascertaining the nature of the disease. 

To determine in any given case whether the quantity of the 
urine is increased or diminished, it is not sufficient merely to 
measure the urine ; we must also know how far the amount 
found exceeds or falls short of the normal quantity. We must, 
therefore, learn the normal quantity passed by the individual. 



446 SEMIOLOGY OF HTIMAN URINE. 

If very accurate determinations are required, as for example in 
physiological experiments as to the influence of different agents 
on the urinary secretion, the normal quantity of urine passed 
by the individual must always be ascertained by trial at the 
time of each experiment. In investigations on the sick, on the 
other hand, we must, as a rule, be content with approximate 
determinations, and substitute for the amount of urine of the 
individual, which usually cannot be determined, the average 
quantity determined by numerous observations on different in- 
dividuals. 

In practice, however, little attention is oftentimes paid to 
this principle ; because, on the one hand, physicians are apt 
to trouble themselves too little with such investigations, and 
hence deduce from observations, quite correct in themselves, 
false conclusions on account of judging them by an incorrect 
standard ; and, on the other hand, over-exact physiologists un- 
justly reject approximate investigations made on patients, be- 
cause they do not appear to them to be sufficiently accurate. 
It seems desirable, therefore, to illustrate this subject by a fev/ 
examples. 

We know that the average quantity of urine passed by an 
adult in health in an hour amounts to from 60 to 70 cc, but 
that it may vary between 30 and 100 cc. If now we find that in 
an individual, the normal amount of whose urine we are not ac- 
quainted with, an average hourly quantity of 80 cc. is passed 
under the influence of some medicinal agent, we may fairly 
conclude that the medicine employed had a diuretic effect ; the 
conclusion, however, is not absolutely certain, because, as we 
have seen, 80 cc. are within the limits of the normal variation 
in the quantity of urine. Still less are we able from this ex- 
periment to decide to what extent the urine has been increased 
by the medicine employed, because the ordinary amount of 
urine passed by the individual may be either somewhat above 
or below the average. To obtain a trustworthy result in such 
a case we must ascertain as accurately as possible, by very 
numerous observations, the average quantity of urine passed by 
the individual at the time of the experiment, and then compare 
the quantity thus obtained with the quantity passed under the 
influence of the medicine. 

If we find, after repeated trials, that a person who has par- 



QUANTITATIVE CHANGES IN THE URINE. 44nf 

taken largely of fluids (water, tea, etc.) passes an average of 
400 cc. of urine per hour, we may be assured, without accurately 
knowing the normal quantity of urine passed by the individual 
in question, that the fluids which have been taken by him have 
had a diuretic effect. The 400 cc. of urine which are passed 
per hour are so much in excess of the average quantity that it 
becomes a matter of no importance whether the average quan- 
tity passed by the individual is 40, 60, or 80 cc. per hour. 

Quite the same thing often occurs in patients. The average 
quantity of urine passed in twenty-four hours by healthy, well- 
nourished adults amounts to from 1,400 to 1,600 cc. ; in those 
who drink a smaller amount of fluid, 1,200 to 1,400 cc. If, there- 
fore, we find that a patient passes only 400 cc. in twenty-four 
hours, we may be sure that the quantity of his urine is essen- 
tially diminished ; the diminution is so considerable that it is 
a matter of small importance to ascertain whether the normal 
quantity of urine passed by the person in question is 1,200 or 
1,400 cc. We may conclude, with equal certainty, that the 
amount of urine is abnormally increased in a patient who passes 
2,500 or 3,000 cc. of urine in twenty-four hours, although we 
have not accurately measured the normal quantity of urine 
passed by that individual. 

Numerous observations show that in healthy adults the ave- 
rage quantity of urine passed is — 

a. In twenty-four hours : 

By well-nourished persons who drink abundantly, 

from 1,400 to 1,500 cc. 

By those who drink less 1,200 to 1,400 cc. 

b. In one hour : ' 

By those who drink freely 60 to 70 cc. 

By those who drink less freely 40 to 50 cc. 

If we calculate the average quantity of urine for the iveigU of 
the body, we find that an adult passes an average of 1 cc. of urine 
per hour for each kilogram (=: two pounds) of the weight of 
his body. 

Calculating according to the Jieight of the body, we find that an 
adult passes hourly 40 cc. on an average for each 100 cm. 



448 SEMIOLOGY OF HUMAN URINE. 

People who do not lead very regular lives are the subjects of 
very considerable fluctuations in the daily and hourly quantity 
of urine. 

The daily quantity may vary between 1,000 and 3,000, and 
the hourly quantity between 20 and 200 cc. 

These variations depend in great measure upon different ex- 
ternal influences, upon the food, and especially upon the drink, 
and upon an increase or diminution of the persj^iration ; and in 
persons who live regularly the variations are confined within 
much narrower limits than in those who live irregularly. 

Moreover, w^e observe tolerably constant variations in the 
hourly quantity of urine at different times of the day. In this 
country (Germany) the average hourly quantity of urine is 
greatest in the afternoon hours, after the chief meal or dinner 
(77 cc. in an hour) ; it is the smallest during the night (58 cc. 
in an hour), and a medium quantity is passed in the forenoon 
(69 cc). We must, therefore, in all cases in which we wish to 
determine accurately the influence of any agent upon the se- 
cretion of urine, take into consideration the time of day at 
which the exjDeriment was performed. 

It is very difficult to answer the question as to what in- 
fluences increase or diminish the quantity of the urine, and 
chiefly because a large number of agents are simultaneously 
at work increasing or diminishing it, and these aid or neutral- 
ize each other, so that it is very difficult to isolate and deter- 
mine the amount of each single influence. 

The secretion of urine is decidedly increased by free drink- 
ing, though certainly not to the extent asserted by Falk, who 
stated that the whole quantity of water drunk is separated by 
the urine. We all know that a person who drinks a great deal, 
when exposed to a high temperature, and at the same time 
takes considerable exercise, sweats profusely, and accurate ex- 
periments have shown that under such circumstances a larger 
portion of the water taken passes out of the body through the 
skin than through the kidneys. The most different fluids, such 
as ordinary water, carbonated water, beer, wine, tea, etc., when 
taken in sufficient quantity, act as diuretics on people in health 
(but not always in disease) ; undoubtedly, however, the differ- 
ences which exist in the diuretic action of the different fluids 
are very difficult to determine accurately, since a large number 



QUANTITATIVE CHANGES IN THE URINE. 449 

of very variable circumstances modify their action, and, more- 
over, individual peculiarity plays an important part. 

Examples. The quantity of urine passed per hour in healthy 
men was increased by plentiful drinking of water from between 
60 and 70 cc. to 300, 400, 600 cc, and even more. 

In twelve students, who, for the sake of experiment, drank 
large quantities of beer, the average quantity of urine secreted 
per hour amounted to 473 cc. ; the minimum quantity was 212, 
the maximum 838 cc. 

C. "Westphal ^ and K. H. Ferber t found that the exhibition 
of water increased the secretion of urine in dogs as well as in 
man, the secretion gradually increasing remained stationary for 
some hours and then returned to the normal standard. They 
also found that the whole of the water which v/as drunk was 
not eliminated with the urine, but that a very considerable 
portion of it always passed off with the perspiration. 

The quantity of urine is diminished by lessening the absorp- 
tion of fluid (abstaining from drink until great thirst is expe- 
rienced), but not in the same degree that it is increased by free 
drinking. 

Example. Four male individuals from 20 to 25 years of age 
were placed on dry' diet. The average hourly quantity of urine 
which they passed, which with ordinary diet was 86 cc, sank 
to 37 cc. (Hosier.) 

All causes which aid the elimination of water from the body 
by other channels diminish the secretion of urine ; especially 
copious sweating, abundant watery stools, and much vomiting. 

On the other hand, all causes which lessen the other watery 
secretions of the body increase the quantity of the urine : much 
atmospheric moisture, which impedes cutaneous and pulmonary 
exhalations, and other agents, such as cold, which diminishes 
the cutaneous perspiration. 

Causes of this sort seldom exert an unmixed influence, so 
that the quantity of urine which is observed in such cases 
can seldom be regarded as a standard of the action of a par- 
ticular agent. For this reason I shall omit numerous examples 
which I might quote. To obtain a general idea of the activity 

* Vircliow*s Archiv, 1860, Band 18, p. 509, et seq. 
f Arch. d. Heilkunde, 1860, i., p. 244, et seq. 
29 



450 SEMIOLOGY OF HUMAN URINE. 

of these influences tlie following considerations may be of ser- 
vice. The quantity of water passed with the urine is about 
equal to the whole amount eliminated by the skin, the lungs, 
and intestines, taken together. If, therefore, an increase or 
diminution of one of these latter functions is to exercise a con- 
siderable influence on the amount of urine, it must necessarily 
be quite a large one. 

The intensity of the activity of the kidney, doubtless de- 
pendent on the nervous system, exerts a very decided influence 
on the quantity of the urine, especially the amount of blood 
pressure existing in the vessels of the kidney. This is gene- 
rally greater during great bodily and mental activity, and less- 
ened during rest and sleep. It is also increased and diminished 
by diff'erent diseases. 

A very large number of observations made on seven men gave 
as the average quantity of urine passed in the night 58 cc, and on 
the other hand 73 cc. as the average during the day. That rest 
alone was the only cause of this difference is shown by the fact 
that persons who work during the night, either bodily or men- 
tally, pass as much urine then as they do during the day. 

The influence of increased action of the kidneys on the secre- 
tion of urine is strikingly shown in cases of dropsy. In a 
dropsical patient who passes on an average only 400 cc. of urine 
in twenty-four hours, the secretion under the influence of diure- 
tics or even by the simple increase of the general strength may 
reach in a very short time 3,000 or even 5,000 cc. per day, with- 
out any essential change in the mode of life, quantity of drink, 
etc. 

If we attempt to formularize the different influences on which 
the quantity of the urine depends, it may be expressed about 
as follows : 

The factors ivhich especially determine the quantity of urine se- 
creted are : 

1. Th£ more or less loatery condition of the hlood. The quantity 
is increased by a free addition of fluid to the blood, and it is 
diminished by an abundant separation of water. 

2. The excretory activity of the kidneys. This is certainly not a 
simple force ; it depends on the degree of arterial blood pressure 
generally, and especially on the tension in the renal arteries, 
particularly the glomeruli ; on the greater or less ease with 



qUANTITATIYE CHANGES IN THE UBINE. 451 

wliicli tlie urine flows from the tiibnles ; on the state of the 
nervous system generally, and on the state of the renal nerves 
in particular, etc. All of these different forces, however, have 
not yet been accurately determined ; we, therefore, group them 
all under the above general expression. 

Quantity of Urine in Disease. 

The quantity of urine passed by the sick frequently varies 
much from the normal. These deviations are sometimes more 
of an accidental nature dependent on various causes; some- 
times they are constant and essential, so that they are always 
the same in diseases of the same kind. The abnormal states 
of the urine of the latter class are of great importance to the 
physician in regard to diagnosis, prognosis, and treatment. 
The most important of these are the following : 

1. At the height of all acute febrile diseases the quantity of urine 
is considerably diminished, except in a few rare instances, as 
during the paroxysms in most cases of intermittent fever, but 
it increases again when the intensity of the disease has passed. 
During convalescence the quantity of urine becomes normal or 
even exceeds this point. 

Hence in all such diseases the quantity, especially in connec- 
tion with the color (see § 122) of the urine, gives important in- 
dications. Thus a constant daily diminution of the quantity of 
the urine indicates that the intensity of the disease is increas- 
ing — a continued low quantity of the urine (below 800 cc. per 
diem) shows that the intensity of the disease has not diminished 
— while a steady increase of the quantity of urine shows that 
the force of the disease has been broken. 

An explanation of this general law, which is of importance 
as regards the state of metamorphosis in febrile diseases, can 
not be given as yet. A careful examination of the urine in all 
of these cases shows that the diminution of the quantity of urine 
depends almost exclusively on a diminished separation of ivater 
by the kidneys ; in what way this is brought about, whether by 
diminution of the blood pressure, by lessening of the nervous 
influence, or by some other unknown circumstances, we do not 
venture to determine. 

This diminution of the quantity of the urine, with very few 
exceptions, takes place in all acute febrile diseases, as pneu- 
monia, pleurisy, typhoid fever, rheumatism, gastritis, pysemic 



452 SEMIOLOGY OF HUMAN UBINE. 

fever, etc., and every physician lias so good and frequent an 
opportimity to observe it, that examples appear to be quite 
superfluous. The following will serve to show the progress of 
the urinary secretion in such cases. 

A., an attendant in my clinic, whose normal quantity of urine 
had been accurately determined for a long time beforehand, 
became ill with typhoid fever. The quantity of urine which 
before averaged about 1,800 cc. daily, constantly diminished 
during three days until it reached 200 cc. ; in the next five days 
it gradually increased up to the normal amount, and then it in- 
creased beyond this to 2,200 cc, and finally gradually returned 
to the normal standard. 

In a patient suffering with pneumonia the quantity of urine 
at the beginning of the sickness diminished to 500 cc, then it 
constantly rose in the course of ten days to the normal standard, 
exceeded this, and reached 3,000 cc, when it gradually returned 
to the normal amount and with slight variations remained nor- 
mal. 

2. Toward ih^ fatal termination of diseases both acute and 
chronic, the quantity of urine frequently either constantly di- 
minishes, or it remains very low for a long time with variations. 
This, however, is not always the case : sometimes the quantity 
of urine diminishes only a little up to the time of death (it re- 
mains over 800 cc per diem). This, without doubt, is due to 
the fact that in many cases the immediate cause of death is a 
gradual failure of nutrition ; while in other cases it is suddenly 
brought about by nervous disturbances, interference with the 
pulmonary or cardiac movements, etc. 

3. The quantity of urine passed in clironic diseases, esj^ecially 
in dropsy and in those cases which are classed under the com- 
mon name of diabetes (better polyuria) , is of especial importance 
to physicians. 

As a rule, in dropsical patients, the quantity of urine, and 
especially the separation of water by the kidneys, is essentially 
diminished. As a result, its constituents, which should be eli- 
minated, especially water, are retained in the blood, and either 
the exudation of watery fluids into the cellular tissue, serous 
cavities, etc, is favored, or the absorption of fluid already pres- 
ent is rendered more difficult. Experience shows that persons 
suffering from dropsy are cured more especially by increasing 



QUANTITATIVE CHANGES IN THE URINE. 453 

tliG secretion of urine (diuretics) ; and the greater or smaller 
amount of urine, as a rule, in dropsical patients, is not only tlie 
safest guide in making tlie prognosis, but it also furnishes indi- 
cations for treatment. 

We usually designate with the name of diabetes those dis- 
eases in which the quantity of urine, for a long time, largely 
exceeds the normal standard. To judge of these cases, how- 
ever, it is necessary to ascertain the amount of the solid con- 
stituents contained in the urine, and not merely the quantity. 
(Compare the following section.) 

In many cases of polyuria the neryous system evidently has 
a great influence on the increase of the urinary secretion. "* 

4. It is self-evident that in the sick all those things must be 
taken into account which may have an influence on the quantity 
of urine in health. Thus, in disease, the quantity of the urine 
may be temporarily increased by free drinking, by a watery 
condition of the blood in combination with an increased activity 
of the kidneys. More frequently it is diminished. Temporarily, 
by sweating, diarrhoeas, and other watery evacuations ; perma- 
nently, as a rule, in consequence of their taking less food than 
people in health, and because the metamorphosis in general is 
diminished. 

§ 121. Solid Eesidue and Specific Gravity of the Urine, t 

1. The methods of estimating the quantity of the solid resi- 
due of urine, its amount of water, and other constituents wdiich 
volatilize at 100'', have been already described in § 59. The pro- 
cesses given there, however, are both tedious and difficult, so 
that they can seldom be used practically ; still we must employ 
them in all cases in which as accurate an estimation as possible 
of the quantity of water or of the solid residue of urine is re- 
quired. 

For the purposes of the physician, who only requires approxi- 
mate results, these processes may be replaced by a determina- 
tion of the specific gravity of the urine, and from this its amount 
of solid constituents may be inferred. This method of deter- 

* See W. Ebstein, Deutscli Arcli. f. Mm, Med., 1873, xi., p. 344, et seq., and 
F. Mosler, Vircliow's Arciiiv, 1873. Ivi., p. 44, et seq. 
f J. Vogel, Arcliiv ftir gemeiuscliaftliclie Arbeiten, i., p. 419, et seq. 



454 SEMIOLOGY OF HUMAN UBINE. 

mining the specific gravity lias been explained in § 58. For tlie 
physician's use the so-called urinometer, a glass hydrometer, is 
the most convenient, as it may be simply allowed to sink in the 
urine which is to be tested. (See page 212.) 

If the urine were a fluid which, independently of its variable 
amount of water, always contained the same constituents in the 
same proportion, we could estimate with tolerable accuracy its 
quantity of solid constituents from its sj)ecific gravity, just as 
the percentage of alcohol or of sulphuric acid is ascertained. 
Unfortunately this is not the case, the quantity of the different 
constituents of the urine increases and diminishes in very vari- 
able proportions ; therefore we cannot obtain from the specific 
gravity of the urine accurate results as to the amount of solid 
constituents, but they are always more or less uncertain. The 
best formula by which to reckon the quantity of solid constitu- 
ents in the urine from its specific gravity is Trapp's. It con- 
sists in doubling the two last figures of the specific gravity ob- 
tained. The product gives the number of grams of solid con- 
stituents contained in 1,000 cc. of the urine in question. Thus, 
a urine of 1*010 specific gravity contains 20 grm. of solid con- 
stituents in 1,000 cc. ; of sp. gr. 1*015, 30 grm. ; of 1*020, 40 grm., 
and so on. 

In order not to draw erroneous conclusions as to the amount 
of solid constituents from the specific gravity of a urine we must 
first of all bear in mind how great the accuracy of this method 
is, and also how great is its liability to error. Numerous ex- 
periments made by myself, and comparison with the observa- 
tions of others, have shown me that, in estimating the solid 
residue of a urine from its specific gravity in specimens of nor- 
mal urine, we may easily have an error of one-tenth, or even 
one-seventh ; and in the urine of the sick, especially when the 
specific gravity is high, the error may be even greater, amount- 
ing to one-fifth or one-quarter. If in three successive days 
there are found 55, 50, and 60 grm. of solid constituents accord- 
ing to Trapp's formula, these differences are so slight that they 
fall within the limits of error in the observations, and we should 
not be justified in saying that the patient on the day on which 
the calculation gave 60 grm., passed the most solid constituents 
with the urine, and on that in which 50 grm. were found, the 
least was passed. Such a conclusion would only be justified 



QUANTITATIVE CHANGES IN THE URINE. 455 

when the quantity of solid constituents of the urine had been 
determined by a more exact method. If, on the other hand, we 
find from the specific gravity that a person who has passed, on 
an average, about 60 grm. of solid constituents with the urine, 
secretes on one day only 30, we are perfectly justified in conclud- 
ing that he has passed on that day much less solid material 
than usual, since the difference is so great that it cannot be ex- 
plained as an error of observation. On the other hand, it 
would be very rash to assert that the person in question had 
passed only one-half the ordinary quantity of solids, and it is 
only to be regarded as approximate, since a direct determination 
would give, perhaps, 28 or 36 instead of 30 grm. 

Since all such determinations of the solid residue from the 
specific gravity give such inaccurate results, it appears to be 
quite immaterial whether we make use of Trapp's cocfiicient (2) 
or of a different one (for example, Hiiser's=2'33, or of Christi- 
son's=2'3), since the difference between them (between Trapp's 
and Hiiser's is only one-sixth) still comes within the limits of 
unavoidable errors of observation. 

W. Kaupp "* also found Trapp's formula correct, while the 
accurate investigations of Neubauer (see page 221, 3, and page 
347) are more in favor of Hiiser's formula. For estimations 
and conclusions at the bedside of the patient, which can never 
be very exact, the coefficient 2 commends itself by its simplicity 
and the readiness with which it can be reckoned in the head. 
In such cases differences in the temperature of the urine, if they 
do not exceed a couple of degrees, may be disregarded. 

2. What practical conclusions can the physician draw from 
the quantity of solid residue and the specific gravity of the 
urine ? 

First the specific gravity enables us to calculate the weight of 
a measured quantity of urine. The calculation is simple : 1*000 
cc. of urine of specific gravity 1*024 weigh 1*024 grm., and so on. 

Further the specific gravity of the urine and the quantity of 
solid constituents found either directly by analysis or calculated 
often give important indications concerning many quantitative 
changes of metamorphosis ; especially in the quantity of solids 
and of water, which have been separated by the urine under 
certain circumstances in a certain time. 

* Arcliiv fiir phys. Heilkunde, 1856, Heft 4. 



456 SEMIOLOGY OF HUMAN URINE. 

To judge of these conditions it is of prime importance for us 
to know the exact normal. 

The average specific gravity of the urine in male adults in the 
normal condition is about 1"020. From this we may reckon that 
in an average daily quantity of urine of 1,400 or 1,600 cc, an 
average daily quantity of 55 or 65 grm. of solid constituents are 
eliminated. 

A man passes on an average 4*1 grm. of solid constituents per 
100 kilograms of weight and 1*5 gTm. per 100 centimeters of 
height per hour. 

These figures form the basis for recognizing and forming an 
opinion of many abnormities of the metamorphosis in disease. 

In most acute diseases the daily separation of solid consti- 
tuents by the nrine is somewhat less than in health ; instead of 
60 it amounts to only 40 or 50 grm. Since such patients as a 
rule, however, only take fluids which contain little solids, they 
are in a condition similar to that of persons fasting, the separa- 
tion of the solid constituents of the urine takes place in them 
at the expense of the body, they consume their own flesh, as it 
were, and become thin. 

The estimation of the amount of solid residue of the urine is 
of especial practical interest in all cases in which the secretion 
is much increased in quantity (polyuria). These cases may be 
separated into two well-marked gToups according to the greater 
or less quantity of solid constituents contained in the urine. 

1. The abundantly secreted urine contains much more solid 
material than in the normal condition, much more in fact than 
is introduced into the body by means of the food. Hence arises 
a disproportion of nutrition, the patients in question become 
wxak and emaciated. The cases belonging to this group are 
included under the further subdivisions according as the urine 
contains sugar (diabetes mellitus), or is free from it but contains 
an abnormally large amount of the other solid constituents 
(diabetes insipidus). 

2. The excessively abundant urine has a low specific gravity 
and contains relatively few solid constituents. Water is the 
constituent which is chiefly separated from the body by it, and 
it is very readily restored again ; no emaciation results, there- 
fore, and no hectic; on the contrary, the process is sometimes 
beneficial, and promotes the removal of diseased products, as in 



QUANTITATIVE CHANGES IN THE URINE. 457 

many cases of liydrsemia and dropsy. Tliis form of increase of 
the urinary secretion (hydruria) must, therefore, be most care- 
fully distinguished from true diabetes. 

Examples. A woman, 31 years of age, who had suffered for a 
long time from symptoms of anaemia and hysteria, with giddi- 
ness, headache, spasms of the cervical muscles, sensitiveness 
of several of the vertebrae, pale face, etc., passed an increased 
quantity of urine (the average of a fourteen days' observation 
amounted to 3,080 cc. daily). The specific gravity of the urine 
was only slightly diminished, and the calculated quantity of 
solid constituents in it amounted to a daily average of 87 grm., 
a quantity much greater than normal (the maximum in 24 hours 
was 136 grm., which was more than double the normal quan- 
tity). In this case, w^hich was one of true diabetes insipidus, 
the increased separation of the solid constituents of the urine 
combined with a deficiency of nourishment was evidently the 
chief cause of the symptoms, which rapidly improved under 
a more generous diet in addition to the use of iron and other 
tonics. 

A man, 35 years old, of herculean frame, suffering from rheu- 
matism of the neck, passed a very large quantity of urine (the 
daily average of observations lasting twenty-four days was 
2,983 cc), but its specific gravity was very low (between 1*005 
and 1*012), and the daily average amount of solid constituents 
reckoned from it amounted only to 42 grm., therefore less than 
normal. This man did not appear to suffer at all from the in- 
creased secretion of urine; it evidently was not diabetes, but 
merely hydruria. 

Many other conclusions concerning the quantitative changes 
of metamorphosis in disease may be drawn from the specific 
gravity and quantity of the solid constituents of the urine ; thus, 
for example, the relation of the amount of solid constituents 
which are eliminated with the urine to that of those which are 
eliminated by the skin and lungs may be ascertained ; when 
the quantity of solid matters taken with the food is known at 
the same time, we obtain the relation of the amount which is 
taken into the body to that which passes out of it, etc. The 
knowledge of all of these points is of great importance in rela- 
tion to the metamorphosis in disease, and the necessary means 
are of such a nature as to be procured in every clinic without 



458 SEMIOLOGY OF HUMAN URINE. 

difficulty ; but so little has been done thus far in this field that 
no sjDecial conclusions have been drawn as yet. 

The specific gravity of the urine, moreover, gives the phy- 
sician indications which, though of themselves not sufficient 
to lead to any definite conclusions in diagnosis, prognosis, and 
treatment, are yet serviceable by leading to further investiga- 
tions. The following considerations belong under this head : 

Urea is the chief solid constituent of the urine as a rule ; it 
usually equals all of the others together and sometimes exceeds 
them. Therefore, the specific gravity of the urine may also 
serve to point out approximately the quantity of urea contained 
in it. Such an estimation of the quantity of urea is, however, 
very uncertain, and considering the ease with which it may 
be directly determined quantitatively it will never replace the 
latter method. 

When urine is far below the normal in quantity and has a 
high specific gravity, we may generally infer in the case of 
healthy persons that its condition depends on abstinence from 
drink or upon an abundant loss of water by increased perspira- 
tion ; and in the case of disease it depends on an acute disease. 
When the amount of urine is increased far beyond the normal 
and the specific gravity is low, we may conclude that an excess 
of fluid has been taken. In the sick who are suffering from 
hydraemia or dropsy such a condition of the urine is a very 
favorable sign, and indicates that the system is making an effort 
to get rid of the excess of water collected in the blood or tissues. 

If a superabundant amount of urine of high specific gravity 
is j)assed, or if it has only the ordinary specific gravity, we 
must bear diabetes mellitus in mind and test for sugar; or, 
when it contains no sugar, the case is diabetes insipidus. 

If the quantity of urine is not increased, or if it is diminished 
even and yet its specific gravity is low, we may suspect the ex- 
istence of some impediment to the secretion of urea, and have 
reason to fear the results of retention of urea in the body 
(ursemia) in ^ich a case. 

In most chronic diseases (except diabetes) the solid residue 
of the urine is diminished ; an increase of the solid residue in- 
dicates a more active metamorphosis and better nutrition, and 
is, therefore, a favorable sign as a rule, 

On the other hand, an increase of the solid residue of the 



QUANTITATIVE CHANGES IN THE URINE. 459 

urine at the height of acute diseases is usually an unfavorable 
sign, because the inanition, which always occurs in such cases, 
is thereby increased and favored. 

The specific gravity of the urine, as a rule, in acute febrile 
diseases, is in inverse proportion to its quantity ; the specific 
gravity increases at the height of the attack in proportion as 
the quantity diminishes ; it afterward falls with the increase of 
the quantity, and sinks during convalescence frequently below 
the normal. We must be careful, however, not to infer too 
much from the specific gravity of the urine alone, and not to 
utilize it, for example, for the differentiation of diseases which 
in other respects present similar symptoms. 

It has been stated that the specific gravity of the urine in- 
creases much less in typhoid than in other acute diseases, and 
especially in inflammatory diseases; and that in the true ty- 
phous stage it amounts to only 1*017, while in acute affections 
of the brain, especially meningitis, from the beginning to the 
end, it is much higher (1'028 to 1'035). This difference, there- 
fore, may be utilized in cases where it is difficult to distinguish 
between a typhoid and such affections of the brain. ^ Such an 
attempt to distinguish diseases by a single phenomenon, and 
one which, in comparison with the other symptoms, is very un- 
important, belongs to the now happily ended ontological method 
of comprehending diseases. In the distinction and classifica- 
tion of diseases by this method, just as in the division of animals 
and plants into genera and species, only the external appearance 
.with its thousand accidents is regarded instead of their essen- 
tial character, their causes, connections, and interdependence 
being kept in view. Such a use of a single symptom can only 
be justified, when not only the fact itself has been surely estab- 
lished by numerous observations, but also its cause and signifi- 
cation have been explained, and its necessary relation with the 
disease in question. 

In the case before us, there is wanting not only a satisfac- 
tory explanation of the diminution of the specific gravity of 
the urine in typhoid, but also the truth of the fact, except in 
isolated cases, is only problematical According to my very 
numerous investigations of the urine of typhoid patients, its 

* A. Ziegler, Die Uroscopie am Krankenbette, Erlangen, F. Enke, 1861, p. 8. 



460 SEMIOLOGY OF HUMAN URINE. 

specific gravity, at least in the cases in wliicli considerable 
fever and a certain degree of reaction is present, was high dur- 
ing the acme of the disease, as the following cases show : 

(The figures in all cases show the specific gravity of the 
whole quantity of urine passed in twenty-four hours during the 
height of the disease. The blanks, which sometimes cover 
several days, arise from the impossibility of always collecting 
the whole quantity of urine passed, unmixed with fseces, in 
patients who frequently pass urine involuntarily with their 
stools. This is a circumstance which renders accurate quan- 
titative examinations of the urine in typhoid at the height of 
the disease difficult or even impossible.) 

Case 1. Third day, 1-019— 1-029— 1-031— 1-026— 1-024— (two 
days omitted) — 1-019 — 1-021 — 1*016. Subsidence of the fever. 
Convalescence. 

Case 2. Fourth day, 1-028— 1-029— 1-027— (one day omitted) 
— 1-028-1-027. Death. 

Cases. Second week, 1-019— 1-020— 1-018-1-020— 1-022— 
1-026. Slow convalescence. 

The specific gravity of the urine in typhoid, as in other acute 
diseases, falls as the fever diminishes and convalesence is es- 
tablished. 

On the other hand, I must admit that there are cases of 
typhoid in which the specific gravity of the urine, even during 
the height of the disease, is low, sometimes even far below the 
normal, as the following examples show : 

Case 1. 1-008— 1-014— 1-017— (two days omitted)— 1 -01 7— 
1-027-1-015—1-014—1-015—1-014—1-012. Death. 

Case 2. First week, 1-018 to 1-020. Second week, 1-012 to 
1*015 ; then convalescence. 

Case 3. 1-021— 1-020— 1-015— 1-014— 1-010— 1-006— 1 -010— 
1-012—1-013—1-015—1-011. Convalescence. 

In all of these cases, however, the fever from the first had a 
distinctly marked adynamic character, and the general condi- 
tion of the patients, especially the weak and distinctly double 
pulse, afforded much more trustworthy signs for distinguishing 
the case from one of inflammatory affection of the brain and its 
membranes than the specific gravity of the urine, which, more- 
over, I have not always found so remarkably high in menin- 
gitis as Ziegier states it to be. Such a diminution of the spe- 



qjJANTITATIVE CHANGES IN THE URINE. 461 

cific gravity of tlie urine, raoreover, does not occur exclusively 
in typhoid ; it also occurs in other forms of fever, when they 
assume a well-marked adynamic character, as in pyaemia, pu- 
trid fevers, etc. 

§ 122. The Quantity of Ueinaey Pigment.^' 

The color of the urine and the pigments which cause it have 
been already spoken of in various places (§ 10, § 61, § 93). It 
is very difficult, indeed almost impossible, to obtain an accurate 
estimation of the quantity of coloring matter in the urine cor- 
responding to the requirements, which we are entitled to ex- 
pect of quantitative chemical analysis at the present day. I 
have, therefore, proposed another method, very simple and 
easy, of determining this substance quantitatively, so that every 
practitioner can avail himself of it. Although the results are 
not absolutely exact, but are merely approximate, they afford 
much that is interesting and valuable for diagnosis, prognosis, 
and treatment. 

This method, and the mode of employing it, has already been 
explained in § 61, and the color table in Plate IV. gives every 
one an opportunity of using it himself. 

As objections to this method, since its proposal, have been 
made by various writers, I will briefly answer them. 

First, it has been objected that the color of the urine does 
not depend on one and the same pigment, but on several differ- 
ent ones. This is correct, and has been already admitted in 
§ 93. But the abnormal colors of the urine described there, 
whether they are merely accidental, depending on the pigments 
of rhubarb, senna, etc., or whether dependent on biliary pig- 
ment, uroxanthin, uroglaucin, urrhodin, and uroerythin, are 
relatively rare, and, when present, may be readily recognized. 
In all such cases it w^ould doubtless be a mistake to use the 
color table for the quantitative estimation of the urinary pig- 
ment. But these are exceptional cases for which the method 
is not adapted ; and it can be no reproach to it that this is the 
case, for it very rarely happens in other quantitative chemical 
investigations that a method is applicable to all cases. In by 
far the greater number of cases the urine, especially when it has 

* J. Vogel, Arcliiv fiir gemeinscliaftliclie Arbeiten, i., p. 137. 



462 SEMIOLOGY OF HUMAN URINE. 

been filtered, contains eitlier none, or only a very small quantity, 
of such abnormal coloring matters, but is usually colored by 
tlie ordinary urinary pigment (Heller's urophgein, Thudichum's 
uroclirom, Jaffa's urobilin). 

Moreover, it lias been objected that the shades of color given 
in the color table do not follow in an exact series, and that by 
diluting brown or very high-colored urine, we should not ob- 
tain exactly the same shades of color which pale urine yields ; 
and, therefore, the statement that a red urine contains thirty-two 
times, and a brown red one sixty-four times as much coloring 
matter as a pale yellow would not be exact. I am quite ready 
to admit that the coloring matter of the urine is not the same 
thing always and under all circumstances, but that it may pre- 
sent modifications which exercise an influence both over its 
coloring power and over the shade of color produced by it ; but 
this is no reason why we should not use the color of the urine 
as a means of estimating approximately the urinary pigment, 
if we do not assume the limits of possible error as too low. 
Hitherto, notwithstanding the praiseworthy efforts of Scherer, 
Harley, Thudichum, Jaffe, and others, we have not been able to 
obtain the urinary pigment in a pure state, so that the estab- 
lishment of the limits of error in this case is completely arbi- 
trary. But I believe I am rather above than below the mark, 
when I assume that the possible error may amount to one- 
fourth or even one-third of the number found. Variations 
which exceed these, therefore, indicate with certainty a differ- 
ence in the amount of coloring matter in two specimens of 
urine compared with each other, while other variations which 
are less than these might be neglected. 

If, for example, the quantity of pigment which a healthy in- 
dividual passes with his urine in twenty-four hours amounts to 
four units, and we find that a sick person passes from sixteen 
to twenty, a considerable increase of the coloring matter in this 
case is undoubted ; it is at least double or treble. There is also 
an undoubted diminution, if the calculation gives only one. 
But if, on the other hand, we should find three and a half or 
four and a half, we cannot conclude with certainty that there 
has been a diminution or an increase. 

On these grounds I consider that I may maintain that this 
method, carefully employed, may give useful results, and that 



QUANTITATIVE CHANGES IN THE URINE. 4^3 

(for tlie reasons given in the following explanation of its signi- 
ficance) it may give the physician very important information 
as to the metamorphosis, or the destruction of blood corpus- 
cles, information which appears the more valuable because the 
means which the physician possesses of forming an opinion as 
to the extent of this kind of metamorphosis in the sick is very 
limited. 

The indication which an increase or diminution of the urinary 
pigment affords to the physician may be derived from the fol- 
lowing considerations, which indeed are not proved, but are in 
part hypothetical, and yet are probably correct. 

There is much reason to believe that a portion of the blood 
corpuscles in the living body is constantly undergoing a retro- 
grade metamorphosis and being dissolved, so that its coloring 
matter, hsematin, is so changed that it finally passes out of the 
body in the form of urinary and biliary pigment ; therefore, we 
have in the amount of the coloring matters of the urine and bile 
taken together a sort of measure of the degree of decomposition 
of the blood corpuscles. From it, in many cases of disease, the 
physician can obtain valuable hints and conclusions respecting 
diagnosis and treatment. 

It is too soon now to be able to determine how much blood 
pigment or how large a quantity of blood corpuscles a certain 
amount of urinary pigment corresponds to. We know too little 
as yet about the changes which blood pigment undergoes be- 
fore it becomes metamorphosed into urinary pigment. For 
this reason I have preferred to take as a standard of compari- 
son for ascertaining the amount of urinary pigment an imagi- 
nary quantity, by fixing 1 as the quantity of urine pigment which 
1,000 cc. of pale yellow urine contains, instead of attempting to 
ascertain the quantity of the coloring matter absolutely by 
weighing or by comparison with the color of a known quantity 
of blood corjDuscles, such a determination in a short time being 
too difficult. 

The reasons for the above hypothesis, that the urinary and 
biliary pigments are modified blood pigment, are as follows : 
Blood coloring matter is very difficult to destroy ; we see that ex- 
travasations of blood in the body, as well as blood which has been 
subjected to various influences outside of the body, retain their 
color with great tenacity, or only undergo slight modifications 



464 SEMIOLOGY OF HUMAN URINE, 

of color. It is not probable, therefore, that the coloring matter 
of the blood which has become unfitted for the purposes of the 
economy is eliminated from the body as a colorless substance, 
but, on the contrary, there can be scarcely any doubt that it is 
still more or less colored when it is excreted. Since the only 
colored excretions of the body are the urine and the stools, we 
must consider the urinary pigment or the biliary pigment (as it 
appears modified in the faeces), or both, as formed from the 
used-up blood pigment. For these reasons many thorough ob- 
servers, as Scherer, PoUi, Yirchow, Harley, and others, have 
not hesitated to regard the biliary coloring matter, the urinary 
pigment, or both, as in part educts of the haematin. Moreover, 
some observers (Hoppe-Seyler, Maly) have recently succeeded 
in transforming blood j)igment (haemoglobin) by chemical treat- 
ment directly into biliary pigment (bilirubin) and urine pigment 
(urobilin). (See page 64) 

The quantity of urine pigment which an adult passes nor- 
mally in twenty-four hours amounts to from 3 to 6 units, or an 
average 4*8, therefore about 0'2 in an hour, the above unit being 
taken as the standard."^ 

According to R. Lawsont a much greater quantity of pig- 
ment is passed with the urine in the tropics (Jamaica), as a 
rule, than in our latitudes : 12 to 14 times the above unit in 
twenty-four hours in healthy men. 

This is the standard for judging the quantity of pigment in 
the urine in a given case of disease, whether it is normal, in- 
creased, or diminished. 

The quantity of urinary pigment is considerably increased in 
all acute febrile diseases in sj)ite of the fact that, at the same 
time, there is a diminution in the amount of urine ; it usually 
reaches 16, 20, and more. This increase in the urinary pigment 
is still greater in fevers which are accompanied by dissolution 
of the blood (typhoid, septic fevers). 

We observe as a general consequence of all of these diseases 

""According to some of my investigations tlie quantity of coloring, matter 
wliicli is passed witli the stools is very variable. I found during twenty- four 
hours from 8 to 30 parts of coloring matter measured according to the above 
scale. 

f Some observations on the urinary and alvine excretions, as they appear with- 
in the tropics, British Rev., Oct. 1861, p. 483, ct seq. 



QUANTITATIVE CHANGES IN THE UBiNE, 465 

a diminution of tlie number of blood corpuscles, a more or less 
anaemic condition of tlie body (more exactly oligocytliaemia). 

Uxamples. In a large number of patients with pneumonia 
the daily quantity of urinary pigment varied between 16 and 
24 units during the height of the disease. In a case of acute 
rheumatism it amounted to between 30 and 32 when the disease 
was at its height ; in a man suffering from typhoid it amounted 
during several days to between 80 and 100 ; in a man who had 
inhaled arseniuretted hydrogen, from 600 to 800. In the last 
case the matter which colored the urine differed somewhat from 
the ordinary urinary pigment, as it was nearly pure hsematin, 
so that its determination quantitatively, according to the inten- 
sity of the color, could only be approximate; the difference, 
however, between the quantity found in these cases and the 
normal quantity is so very great, that an error in the estimation 
of one-quarter or even of one-third need scarcely to be taken 
into account. 

On the other hand the quantity of urinary pigment in many 
diseases is decidedly below the normal, in those cases in which 
a diminished metamorphosis of the blood corpuscles must be 
assumed to exist ; as in many cases of chlorosis and anaemia ; 
in convalescence from severe diseases ; in hysteria and nervous 
diseases, etc. In such cases the character of the urine fre- 
quently serves as an aid in the diagnosis and treatment, since 
tonics, especially preparations of iron, are usually indicated. 

Examples. The daily quantity of urinary pigment in chlorotic 
persons is frequently below 1 ; in convalescence from severe 
diseases it is often for a long time not above 1 or 2, etc. 



II. QUANTITATIVE ALTERATIONS OF THE URINE WHICH REQUIRE 

A COMPLICATED CHEMICAL ANALYSIS FOR THEIR 

DEMONSTRATION. 

§123. 

The quantitative alterations of the urine considered in the 
previous sections are very easily determined, and their estima- 
tion requires so little practice and special knowledge, so little 
apparatus and accessories, that, in point of fact, it is not too 
much to ask that every physician should undertake the investi- 
30 



466 BEMIOLOGY OF HUMAN UBINE. 

gation of tliem liimself, in tliose cases where it is of importance 
to determine these changes of the metamorphosis and to draw 
conclusions from them. 

The quantitative alterations in the composition of the urine 
which are to be spoken of now, have been hitherto much 
more difficult to determine; for the most part they required 
much time, more in fact than the busy practitioner could 
give to them, and presupposed special chemical knowledge 
and a certain practice in quantitative chemical analysis, be- 
sides requiring manifold apparatus, utensils, and reagents. 
Many of them, indeed, could be carried out with the requisite 
certainty only in a completely furnished laboratory, which 
is rarely at the command of a physician. Consequently, ana- 
lyses of this kind have hitherto been undertaken almost solely 
by chemists for the solution of physiological questions, and 
rarely by physicians for practical purposes. Moreover, the 
report of such investigations has been regarded by most 
practitioners as no essential contribution, nor as a necessary 
part of the history of the disease 'in question, but as a super- 
fluous embellishment ; indeed, by many it is regarded as cjuite 
an unnecessary extravagance. Under these circumstances it 
was useless to expect physicians to undertake such investiga- 
tions. Only a few voluntarily applied themselves to it, partly 
through love of science, and partly because they were con- 
vinced that, by undertaking them in some cases of disease en- 
trusted to them, they might render important service. 

Happily this state of things has essentially changed in the 
last few years. Jointly with the ever-increasing application of 
chemistry to the arts and manufactures grew the discovery of 
methods which essentially simplified and shortened quantita- 
tive chemical analyses. These methods, especially the so-called 
volumetric methods, are very well adapted to the purposes of 
the physician. This applies especially to the quantitative ex- 
amination of urine. These simple methods of quantitative 
analysis are already completely worked out for many of the 
constituents of the urine, and we may hope that they will be 
speedily extended to the rest. In short, most of the quantita- 
tive examinations of urine, which a few years ago were difficult 
to perform, are now so simplified that they exceed neither the 
knowledge, skill, nor expedients which we may expect a physi- 



QUANTITATIVE CHAKOES IN THE URINE. 467 

cian to 230ssess. Even want of time can no longer serve as an 
excuse for a physician for neglecting sucli investigations in 
cases where they are necessary, since a chemist or an apothe- 
cary can be found almost anywhere, who, for a small sum, will 
undertake the simplified analysis for the physician; and, in 
case of need, any apt attendant on the sick, or servant, if he be 
careful and intelligent, maj^ be taught in a short time enough 
for the purpose. In many cases, indeed, the patients them- 
selves are not only inclined, but are also qualified to undertake 
such investigations. 

The chief point for the physician who undertakes such ana- 
lyses, or causes them to be undertaken, is that he should always 
clearly know, as far as possible in each case, what he wishes 
and may expect to ascertain by the examination. Any one who 
is not quite clear on this point would do better to give up such 
investigations entirely, since, in such a case, the analysis is 
generally useless and often even mischievous. The chief ob- 
ject which has been in my mind in the following sections has 
been to instruct the physician upon these points, as fax as it is 
possible to do so at the present time. 

I must first, however, before considering the special investi' 
gations of the individual constituents of the urine, premise cer- 
tain general rules which are more or less applicable to all such 
quantitative examinations. They form the contents of the next 
section. 

§ 124. Geneeal Eules foe Quantitative Analysis of the 

Ueink 

1. Hitherto observers have usually made use of an indefinite 
quantity of urine for quantitative estimations, and have been 
satisfied when they had ascertained how much urea, uric acid, 
chloride of sodium, etc., etc., was contained in 1,000 parts. And 
at the present time, also, such analyses of the urine are quite 
often sent or brought to me by patients who come to consult 
me about themselves. From such an analysis, however, we 
learn nothing more than the relation which the single constitu- 
ents of the urine bear to each other. It is, therefore, rarely of 
much service to the physician. And if such a quantitative 
analysis only includes a single constituent of the urine, so that 
we only learn from it how much urea, or uric acid, etc., 1,000 



468 - SEMIOLOGY OF HUMAN URINE. 

parts of tlie iirine contain, it is wliolly useless. A quantitative 
analysis of tlie urine gives a measure of the metamorpliosis 
only wlien, together with the relative quantities of the various 
constituents of the urine, the time is also given during which 
they were passed ; so that we must not only learn how much 
urea, uric acid, etc., are contained in 1,000 parts of urine, but 
we must also know what quantity was passed in a certain time, 
as in twenty-four hours, one hour, etc. Hence, the first requi- 
site in every quantitative analysis of the urine is the determina- 
tion of the time during which it has been passed. This deter- 
mination is very easy in certain patients. Either the urine of 
one day (twenty-four hours) is collected, when it rarely hinges 
on a quarter of an hour, more or less, or the patient carefully 
observes the quantity of urine secreted during a sliorter inter- 
val. If, for example, the patient passed his urine at eight o'clock 
and it was not preserved, and at ten o'clock he passed a fresh 
quantity which was measured and subjected to quantitative 
analysis, we know that the whole amount of the different con- 
stituents of the urine found by the examination were derived 
from a two hours' secretion, and from it we can easily calculate 
how much urea, uric acid, chloride of sodium, etc., were passed 
in one hour, or in any given time. The determination of the 
quantity of the urine, and the time during which it was passed, 
therefore, forms the basis of all quantitative urinary analyses, 
and we cannot recommend the physician too strongly to pay 
the greatest care and attention to these fundamental determina- 
tions, because, if they are inaccurate, all attention and pains 
which have been expended on the analysis have been thrown 
away. The determination of the quantity of the urine passed 
in a given time is difficult and uncertain in many cases, espe- 
cially in the sick ; sometimes the time cannot be accurately as- 
certained, more commonly an uncertain quantity of urine is lost 
by being passed at stool, or involuntarily when the patient is 
seriously ill ; often some is thrown away by the fault of the at- 
tendants or nurse while the physician is absent. The physician 
must know and guard against all of these sources of error, and 
in cases where he is not certain that they can be avoided, it is 
better to dispense with a quantitative analysis of the urine alto- 
gether rather than to run the risk of arriving at erroneous con- 
clusions by starting with false premises. 



QUANTITATIVE CHANGES IN THE URINE. 469 

2. It is very important, moreover, tliat the physician should 
know the limits of error of the different methods which he makes 
use of in the analysis, and should always bear them in mind 
when drawing his conclusions. I will give these limits of error, 
as far as it is possible at present, in each individual case, but 
do not consider it superfluous to make a few general remarks 
on the subject here. 

The limit of error in an analytical method, that is, the quan- 
tity by which the result thus obtained may differ from the 
truth, depends on two circumstances : 1. On the accuracy of the 
method itself ; 2. On the greater or less skill and care of the 
analyst himself, the completeness of his apparatus, purity of 
his reagents, etc. The first is unavoidable, but may be deter- 
mined with tolerable accuracy, and its amount shows the greater 
or less utility of an analytical method. The second circumstance 
is variable ; when the analysis is bad the error is great, when 
it is good it is very small indeed. We cannot expect of every 
physician who performs a quantitative analysis of urine that he 
shall be an expert analyst, but we may require him to have an 
approximate idea of the reliability of his analysis. Any one can 
readily ascertain this by repeating a quantitative estimation of 
the same constituent of urine several times with the same ma- 
terials and following the same method. The greater or less 
degree of conformity which the different analyses exhibit, gives 
an idea at the same time of the reliability of the method em- 
ployed and of the accuracy of the analyst ; it shows how far 
the figures he finds are to be relied upon, and to what extent 
his conclusions are to be accepted. If, in this way, by repeated 
experiment, we have once fixed the limit of error which can be 
committed in an analysis, we may, in cases in which great ac- 
curacy is not necessary, content ourselves with a single uncon- 
trolled analysis. In all quantitative analyses, however, where 
great accuracy is required, where the material admits of a repe- 
tition of the analysis, a second analysis to control the first is 
always to be made, and if the results differ very much, still a 
third, and the average of the results is then to be taken. 

Frequently cases occur where an accurate determination of 
the quantity of constituents of the urine is not necessary for 
practical purposes ; where, in fact, it is quite enough to know 
that a specimen of urine contains more or less than a cer- 



470 SEMIOLOGY OF HUMAN UBINE. 

tain amount of any constituent. A few examples will illus- 
trate this. A healthy man passes about 10 to 13 grm. of chlo- 
ride of sodium with his urine in twenty-four hours. In most 
acute diseases during their height the separation of the chlo- 
ride of sodium by the kidneys is reduced to a minimum. If, 
therefore, we learn by an approximate analysis (which will be 
explained later) that less than 1 grm. of chloride of sodium is 
passed with the urine in twenty-four hours, we may conclude 
that there is a very considerable diminution in the separation 
of chloride of sodium : in many cases this is quite sufficient for 
the purposes of the physician, and it is of no importance to 
know whether the quantity of chloride of sodium amounts to 
0*1 or 0*5 or 0*8 grm. A healthy man passes in an hour about 
0*070 to O'lOO grm. of sulphuric acid with the urine. If we find 
by a simple experiment that a person passes more than 0*400 
grm. in an hour, we can conclude that the separation of sulphu- 
ric acid is very much increased, and that the quantity amounts 
to at least four times the normal standard. 

Such approximate determinations, which may be variously 
modified according to circumstances, have the great advantage 
to the j)hysician that they can be conducted in a very short 
time, within two or three minutes, while an accurate estimation 
would require perhaps thirty or forty minutes. However, we 
must draw no further conclusions than those which the results 
warrant. 

It appears from this that the quantitative analysis of urine 
may and must be carried out in very different ways according 
to our object. A physician who knows what he wants may in 
certain cases draw conclusions from an approximate quantita- 
tive analysis performed in a minute or two, which are more 
valuable to him than the results obtained by a careful analysis 
conducted by a skilled chemist who perhaps has devoted several 
days to the operation, but which is useless to the physician 
because just that point which he wanted to know has been 
omitted. This shows how important it is to keep clearly in 
mind the object aimed at. 

3. The question as to the significance to the physician of 
the increase or diminution of this or that constituent of the 
urine will be answered under the head of each constituent. 
It appears advisable to me, however, to premise here a few 



QUANTITATIVE CHANGES IN THE URINE. 471 

general remarks wliicli are equally applicable to several eon- 
stituents. 

The different constituents of urine may be divided into two 
great classes, according to their origin. 

Those of the one class are doubtless formed within the body ; 
they are in fact the products of the activity of the body. Urea 
and uric acid, which are very rarely taken into the body as in- 
gesta, belong liere. A diminished quantity of these bodies in 
the urine always shows that they have either been produced in 
less quantity than normal, or that they are stored up and re- 
tained in the economy ; perhaps also in a few rare cases they 
have been eliminated in an abnormal way, or have undergone a 
partial decomposition and transformation within the system. 
On the other hand, their increased secretion with the urine 
shows that they are either produced in larger quantity than 
normal, or that they have been stored up somewhere in the 
body and have all at once been eliminated. 

Most of the constituents of the urine belong to the second 
class; they may be produced within the system in part, or be 
formed from other matters by chemical decomposition ; some 
of them only go through the body, however, and whether 
greater or less quantities of them are passed with the urine 
depends in part on the varying activity of the body, and in part 
also on whether greater or less quantities of them are taken 
into the body with food, drink, medicine, etc. Thus, for ex- 
ample, the oxalic acid of the urine, as described in § 110, may 
be formed within the body from other substances, or it may 
have been taken in with food containing oxalic acid. Tlie 
sulphuric acid of the urine may result from the oxidation of 
the sulphur contained in the protein substances and constitu- 
ents of the body, or it may come from sulphate of calcium con- 
tained in drinking water, etc. And whether the urine contains 
more or less chloride of sodium, may depend upon an increase 
or a diminution of the action of the kidneys, or upon the ad- 
dition of a greater or less quantity of salt to the food. 

When, therefore, an increase or diminution of the constitu- 
ents of the urine belonging to this class is found, we must be 
very careful in drawing our conclusions, and must only refer 
the cause to a change in the activity of the system or to its 
pathological conditions, when we are convinced that the in- 



472 SEMIOLOGY OF HUMAN URINE. 

creased or diminisliecl secretion does not depend upon a greater 
or less absorption. Such a conviction can only be obtained 
by determining quantitatively, or at least estimating approxi- 
mately, liow much of the compound in question was taken into 
the body in a given time by the different ingesta. Such investi- 
gations are very laborious and have hitherto been very rarely 
undertaken. Therefore, this whole subject is still shrouded in 
darkness, and the statements which have hitherto been made 
by different observers concerning the increase or diminution of 
single constituents of the urine in diseases must be received 
with a certain amount of caution. 

Finally, we will allow a place here for an observation which 
has been omitted in previous editions as unnecessary, because 
it appears self-evident to every intelligent j)erson, but which 
perhaps is not superfluous, since experience has taught us that 
it has often been neglected and still continues to be. 

When w^e wish to determine alterations of the urine of a 
general nature, as, for example, those which are produced by 
certain influences, certain diseases, etc., very numerous observa- 
tions are necessary as a basis, if the conclusions drawn from 
them are to be in a measure exact and of scientific value. Only 
in those cases in which all of the observations without excep- 
tion show a very considerable deviation from the normal, and 
always in tlie sajne direction, as, for example, diminution in the 
quantity of urine in febrile diseases (see page 451), is a mode- 
rate number of observations sufficient. On the other hand, the 
less the deviations are from the normal, so that they in part 
fall within the limits of the necessary errors of observation, 
and the less these deviations folloAV each other in the same 
direction but appear sometimes positive and sometimes nega- 
tive, the greater must be the number of observations instituted ; 
and in very complicated cases, in which at the same time many 
influences of different sorts act on the urinary secretion, some- 
times thousands of examinations do not suffice to establish a 
''law." 

Any one, who, heedless of this precaution, inconsiderately 
draws conclusions from a few investigations whose results are 
very easily influenced by accidental circumstances, does not con- 
tribute to science, but rather brings confusion into it, and has 
himself to thank when he receives a well-merited rebuke. 



QUAI^TITATIVE CHAjSTGES ZzY THE URINE. 473 

We now turn to the special consideration of tlie indications 
presented by the increase or diminution of the different con- 
stituents of the urine. 

§ 125. Ueea.^^ 

The mode of determining the quantity of urea in the urine 
and the modifications of the process necessary in certain cases 
have been already described fully in § 65 ; it remains for us 
here only to consider the accuracy and limits of error of this 
method, as well as the information which may be obtained from 
the results. 

It seems to be very uncertain, and may lead to considerable 
error, to calculate the quantity of urea in a specimen of urine 
from its specific gravity according to certain formulas as re- 
commended by some authors, for example, Haughton. (See 
page 455.) 

I. The estimation by Liebig's method is certainly the most 
convenient, and, therefore, is to be recommended, especially for 
the purposes of the physician. It .is very accurate, so that 
comparative analyses undertaken with the same urine, and very 
carefully performed, gave a difference of less than one per cent. 
There are two sources of error, however, in this method of de- 
termining the quantity of urea, which in certain cases may lead 
to considerable inaccuracy, and they can only be avoided by 
quite troublesome and long modifications of the original method. 
They are as follows : 

1. The error which depends on the presence of chloride of 
sodium in the urine. 

This, together with the means of avoiding it, have already 
been pointed out on page 237, et seq, I have, therefore, only a 
few practical remarks to make on this point. In all cases in 
which we wish to obtain a very accurate estimation of the 
quantity of urea in a specimen of urine, where an error of one 
or two per cent, is not admissible, we must precipitate the 
chlorine from the urine by nitrate of silver, as described on 
page 238, et seq., before estimating the urea. 

In estimations in which so great accuracy is not required, 

* Th, L. W. Bischoif , Der Harnstoff als Maass des Stoffwechsels, Giessen, 
1853. Voit, Zeitsclir. f. Biologic, Band 4, p. 77, et seq. 



474 SEMIOLOGY OF HUMAI^ UBINE. 

tliis tedious process may be omitted ; then two courses remain 
to us : 

First, we may take no account tvhatever of the chloride of so- 
dium which is present. "We then, except in the cases where 
there is no chloride of sodium at all, or merely traces of it, 
always obtain too high a figure for the urea. The error may 
amount to 10 or even 20 per cent. It will be great, for instance, 
if we compare the urine of healthy people, which usually con- 
tains an abundance of salt, or of persons suffering from chronic 
diseases, with the urine of those who are suffering from acute 
diseases, which usually contains very little chloride of sodium. 

Or we may make a correction for the amount of chloride of 
sodium in the urine in the quantity of urea which has been 
found. (See page 238.) Such a correction, however, is always 
merely approximate, and the error may reach as high as five 
per cent, and be either positive or negative. 

2. A second source of error in the Liebig process is that 
other matters than urea may be precipitated, in which case the 
w^eight of the urea obtained will be too high. 

This is true of allantoin, kreatinin, and sarkosin (see page 
241) ; it is also true of other nitrogenous constituents of the 
urine, which are more frequently present, especially in the 
urine of the sick. Kletzinsky "^ found in a number of carefully 
jDerformed experiments that a nitrogenous compound, which 
was not urea, was precipitated by an acetate of lead solution 
from most urine, but in Liebig's method was precipitated with 
the urea and is included with it in the calculation. The quan- 
tity of this substance in the experiments of K. amounted to 4, 
3, 3, 2, and 2 per cent, in healthy urine ; in the urine of sick 
people, on the other hand, it was much greater (amounting to 
about 12 per cent.). Hence too high a number for the urea, 
especially in the urine of the sick, may be found, and this error, 
in many cases, can probably reach as high as 20 per cent. This 
error is often, to a certain extent, counterbalanced, since the 
urine in acute diseases may contain very little chloride of so- 
dium, and, therefore, the amount of urea found in it, compared 
with that found in the urine of persons in health, without cor- 

^ See Kletzinsky, Komparative Versuclie iiber den Wertli verscliiedener Me- 
tlioden der Harnstoffbestimmung, Heller's Arcliiv, 1853, p. 353. 



QUANTITATIVE CHANGES IN THE URINE. 475 

rection for tlie cliloride of sodium, would be too small; butsucli 
compensations suffice only in very superficial inyestigations, 
and are not reliable when absolute accuracy is required. 

To avoid this error, we must add to the urine under examina- 
tion sugar of lead solution, rendered acid by a drop or two of 
acetic acid, until the whole of the substances capable of pre- 
cipitation are separated ; then any excess of lead is precipitated 
from the filtrate by sulphuretted hydrogen and the urea deter- 
mined by Liebig's method. 

II. "What conclusions are to be drawn from an increase or 
diminution in the quantity of urea in the urine ? 

Naturally the quantity of urea which is separated under nor- 
mal conditions by people in health, forms the basis of such 
conclusions. Numerous investigations, carried on by different 
persons, have shown that a well-nourished, healthy, adult man 
passes, on an average, from 25 to 40 grms. of urea in twenty- 
four hours, and from I'O to 1*66 grm. of urea in one hour. 

Thus, calculating for the weight of the body, it follows that 
from 0*37 to 0*60 grm. are passed, on the average, in twenty- 
four hours, and from 0*015 to 0*035 grm. are passed in one hour 
for every kilogram of weight of the body. 

The absolute quantity of urea passed by women, and, of course, 
also by children, is somewhat less. On the other hand, the 
relative quantity of urea passed by the latter, in proportion to 
the weight of the body, is greater than in adults. According to 
the computations of Ulile,^ children pass in twenty-four hours, 
for each kilogram of weight : 

Children from 3 to 6 years of age, about 1 -0 grm. of urea. 

e( a g a Y\_ ''' ^' ''' '' 0*8 ^^ '^ ^' 

'' "13^^16 '' '' '' '' 0*4 or 0*6 grm. of urea. 

These normal averages are naturally somewhat variable in 
different people, and also in the same person at different times, 
according to the bodily constitution, variety of diet, and greater 
or less activity of metamorphosis. Moreover, they do not in- 
clude the maximum and minimum quantities of urea in certain 
cases in perfectly healthy individuals. 

Food, especially, has a decided and very great influence on 

* Wiener medic. Woclienschr. , 1859, 7 to 9. 



476 SEMIOLOGY OF HUMAN URINE. 

the quantity of urea excreted. More urea is passed with a 
purely animal diet than with a mixed diet ; and more with a 
mixed than with a vegetable diet ; least of all is passed during 
complete abstinence from food. 

The observations of O. von Franque "^ give a very intelligible 
idea of the degree of this influence. He j)assed in twenty-four 
hours : 

With a purely animal diet, 51 to 92 grm. of urea. 

'' '' mixed '' 36 " 38 '' " " 

'' '' vegetable '' 24 '' 28 '' " '' 

" " non-nitrogenous " 16 ^' ^^ '^ 

The importance which urea has for the physiologist and phy- 
sician is that it forms an approximate measure of the meta- 
morphosis of the protein compounds which exist in the body, 
and thus we find the quantity, not of the whole metamorphosis, 
but at least of a very important part of it. 

Although the urea of the body comes originally from the 
protein substances, yet it does not spring directly from them. 
Yarious intermediate bodies are first formed by the metamor- 
phosis, some of which yield urea more readily than others. 
(See page 4) In certain processes of the metamorphosis, espe- 
cially pathological ones, other substances instead of urea, as 
leucin and tyrosin, are formed. (See § 133.) 

Whatever increases the metamorphosis of the protein sub- 
stances, as a rule, increases the urea, and vice versa; therefore, 
the production of urea is in general rather greater during the 
waking hours than during sleep ; it is increased by a rich, 
largely animal diet, and diminished by a sparing, or largely 
vegetable diet ; it increases and diminishes with the degree of 
activity of the body and the mind. Therefore, the quantity of 
urea may be increased or diminished in perfectly healthy indi- 
viduals by a variety of influences, which we will not consider 
any further here. 

The quantity of urea passed with the urine in a given time 
does not depend alone upon the amount of urea produced, but 
also upon whether the urea formed in the body is completely 

* Beitrage zur Kentniss der Harnstoffaussclieidung beim Mensclien, Inaug. 
Abhandl., Wiirzburg, 1855. 



qua:^titativb changes m the urine. 477 

separated or partially retained in the blood and parenchyma- 
tous fluids. Hence, the quantity of urea increases tempora- 
rily with the increase of the urinary secretion, and diminishes 
when it lessens. 

The quantity of urea in disease depends on similar conditions. 

A long-continued increase of the urea in the sick, always in- 
dicates increased conversion of the nitrogenous elements. A 
temporary increase of the urea, however, may depend on an in- 
crease of the urinary secretion, by which the urea collected in 
the body is quickly passed off, and does not necessarily indi- 
cate an increased production of urea. 

A diminution of the quantity of urea may depend on : 

a. A diminution of the protein metamorphosis. 

b. A retention of the urea in the body (as in uraemia, and 
dropsy). 

The secretion of urea in all acute febrile diseases (pneumonia, 
typhoid fever, etc.) has naturally the following course : 

At the commencement of the attack, and until the acme of 
the fever has been reached, the quantity of urea is generally 
increased, sometimes up to 50, 60, and even 80 grm. in twenty- 
four hours, and this in spite of a simultaneous low diet, and 
accompanying diminution of the quantity of urine. This in- 
crease of the urea, however, does not always keep pace with 
the increase of the bodily temperature. 

Later, when the fever diminishes and the increase of meta- 
morphosis has ceased, and while the continued disturbance of 
the appetite causes a diminished ingestion of food, the quantity 
of urea sinks below the normal. 

During convalescence the quantity of urea gradually returns 
again to normal. 

This regular course is naturally variously modified by indi- 
vidual circumstances. 

In intermittent fevers the excretion of urea is markedly in- 
creased during the paroxysm of fever. This increase commences 
before the occurrence of the cold stage, which is important 
with respect to the theory of the fever. 

In most chronic diseases, which are accompanied by a dimi- 
nution of the tissue metamorphosis or of the nutrition, the 
quantity of urea sinks below the normal. During intercurrent 
exacerbations, hectic fever, etc., it is increased again. 



478 SEMIOLOGY OF EJJMAN URINE. 

Tlie quantity is the least when diminished metamorphosis 
occurs at the same time with diminished action of the kidneys. 
For this reason, toward the fatal termination of many diseases, 
it is frequently very small (5 or 6 grm. daily). 

In dropsical conditions it is frequently very much diminished, 
a portion of the urea being dissolved in the dropsical fluids and 
thus retained in the body. When, on the other hand, the se- 
cretion of urine is rendered abundant in such patients by the 
action of diuretics, or by a spontaneously increased activity of 
the kidneys, the secretion of urea will sometimes be considera- 
bly increased for a time, and then much more urea will be 
passed than is produced at the time. The excess of the excre- 
tion over the joroduction arises from the supply stored up in 
the body. 

If for a long time much less urea than normal is passed with 
the urine, we have reason to fear that uraemia may result from 
the retention of urea in the blood. Yet those cases are to be 
judged differently in which the urea is diminished in the urine 
or even wholly absent, because leucin and tyrosin are formed in 
its place, as in acute atrophy of the liver. (See § 133.) 

Urine which contains a large quantity of carbonate of ammo- 
nium, which results from the decomposition of the urea, natu- 
rally contains relatively less urea than normal ; the amount of 
urea, therefore, in strongly ammoniacal urine is no sure criterion 
of the quantity of urea produced. The method which must be 
followed in such cases in order to determine the urea is given 
on page 240. 

The folloAving examples will serve as explanations and proofs 
of the conditions given above : 

A. In health 

A large number of estimations of urea, made according to 
Liebig's method, without correcting for the chloride of sodium, 
gave the following figures for strong, healthy men on good diet : 

1. In H., average quantity of urea per hour, .... 2'13 giTQ. 

2. ** M., " '' .....<*. .... 1-47 " 

3. "J., " *' " " " '* 1st series of experi- ) 

ments, summer, 1852, ) 

4. " J., '* " " " " " 2d series of experi 

ments, Oct., 1853, 



1-66 

1-86 



The numbers given under 2 to 4 are the averages of a largo 



ternoon. 


Night. 


1-58 


1-2 


1-71 


1-61 


1-82 


1-73 



QUANTITATIVE CHANGES IN THE URINE. 479 

number (far more than a hundred) of observations ; consequent- 
ly they represent pretty accurately the average production of 
urea in the individuals referred to at the time the experiments 
were conducted ; they are all, however, somewhat too high (pro- 
babl}^ about 10 per cent.), because the chloride of sodium was 
not precipitated from the urine. 

On account of the large number of the above single observa- 
tions they may also serve to indicate the amount of urea pro- 
duced at different times of the day. The hourly quantity of 
urea amounted to : 

Morning. 
InM., . . 1-7 

'^ J., 1852, . . 1-68 
'' ^' 1853, . , 2-12 

From this it appears that the amount of urea produced at 
different times of the day does not show much variation ; only 
during the night it was a little less than during the day in every 
series of experiments. Observations on the same individual at 
different times of the year (in J., in summer, 1852, and in Octo- 
ber, 1853) likewise show a tolerably great uniformity. 

To give an idea of the amount of the variations which the 
hourly secretion of urea in healthy persons may present, I will 
give the maximum and minimum of the hourly excretion of 
urea in each of the above series of experiments : 

Maximum. Minimum. 

1 3-12 1-54 

2 2-45 0-88 

3 3-41 1-05 

4. . . . . . 2-82 0-89 

B. In disease. 

In TyjjJioid Fever. During the height of the disease the daily 
quantity of urea varied between 40 and 55 grm. As the fever 
diminished, it gradually fell to 20 grm., and during convales- 
cence gradually rose again to the normal. In a case of typhoid 
which terminated fatally, the quantity of urea during the height 
of the fever amounted to 35, 40, and 50 grm ; it fell gradually as 
the disease approached a fatal issue to 25, 20, 10, and during the 
last twenty-four hours before death amounted to only 5 grm. 

In Pneumonia. During the height of the fever the quantity 



480 SEMIOLOGY OF HUMAN URINE. 

of urea increased to 50, 60, and even 70 grm., falling as the 
fever diminished to 25 and 20, and rising again during convales- 
cence. 

In a case of disease of the heart with dropsy the daily quan- 
tity of urea was for some time below the normal, 20, 25, and 28 
grm. As the amount of urine was increased by diuretics, the 
quantity of urea also daily increased to 50 or 60 grm., but it 
fell again as the diuresis ceased. This state of things was 
several times repeated. 

In a patient with rigid arteries and emphysema of the lungs, 
and who also suffered from an intercurrent attack of acute 
bronchitis with oedema of the lungs, the quantity of urea was 
generally small, below 30 grm. "With the occurrence of urse- 
mic symptoms the quantity fell to 12 and even 10 grm. ; under 
the influence of diuretics it temporarily rose again to 25. Then 
came a new collapse with simultaneous diminution of the quan- 
tity of the urine and of the urea (to 11 grm.), and death. 

During the last few years a large number of investigations 
respecting the quantity of urea secreted in different diseases 
have been published. They confirm in all main particulars 
the above general statements already published by me ; which 
statements were based on very numerous observations made 
by me in the clinic at Giessen, in part before the publication 
of Liebig's method, at the instigation and with the assistance 
of my revered friend. A closer study here of the relation of 
the secretion of urea to particular diseases would lead us too 
far ; that belongs to special pathology."^ 



* Those who wish to pursue the subject further will find the most important 
literature as follows : Alfred Vogel (Henle and Pfeuffer Zeitschr., N. F. iv. 
3). S. Moss (ibid. vii. 3). W. Brattler, Ein Beitrag zur Urologie, Miinchen, 
Palm, 1858. (All of these three works treat of the secretion of urea in dif- 
ferent diseases.) W. Miiller iiber HarnstofEabsonderung, etc., nach operativen 
Eingriffen (Wiss. Mittheil. d. Erlanger physik. med. Societat, 1858, Heft 1). R. 
Sander, HarnstofEausscheidung bei paralyt. Blodsinn (Virchow's Archiv, 1858, 
p. 160). F. S. Warneke, Harnstoffausscheidung im Typhoid (Bibl. for Laeger, 
xii. , p. 330). Desgl. im Wechselfieber ; Traube und Jochmann (Deutsche 
Klinik, 1855, Nro. 46). Sidney Einger (Med. chirurg. transact., 1859, p. 
360, et seq., Desgl. in der Cholera; Fr. Lehraann (Inaug. Diss., Ziirich, 1857). 
Traube (Berl. klin. Wochenschr., 1864, 17), Ueber vermehrte HarnstofEpro - 
duction in fieberhaften Krankheiten. E . Unruh (Virchow's Archiv, 1869, 48, 
p. 227, et seq)., Ueber die Stickstoffausscheidung bei fieberhaften Krankheiten. 



QUANTITATIVE CHANGES IN THE URINE. 481 

§ 126. Ueic Acid.^ 

The quantitative estimation of uric acid is to be made ac- 
cording to the method described in § 73. In all cases in which 
the urine contains a sediment of uric acid or urates — and it is 
just in these cases that the quantitative estimation of uric acid 
has the most interest for the physician — we must naturally 
either employ the whole quantity of the urine in its estima- 
tion (in case it should not succeed the sediment is to be 
dissolved again completely by heat), or the urine must be 
filtered and the precipitated uric acid which remains on the 
filter, as well as that in solution in an aliquot part of the fil- 
trate, must be determined, and then the whole quantity of 
uric acid contained in the urine calculated from these two 
together. But such an exact quantitative estimation of the 
uric acid is tolerably tedious and troublesome, and will rarely 
be undertaken, therefore, practically by physicians, who will 
usually content themselves with judging from the presence of a 
sediment of uric acid or urates in the urine how much the 
quantity of uric acid in it exceeds the normal amount. Such a 
conclusion, however, is not reliable ; a sediment of urates fre- 
quently occurs without the quantity of separated uric acid ap- 
pearing absolutely (that is, in a given time) increased. (See 
§ 107.) 

When we have determined the quantity of uric acid in the 
urine, the next thing naturally is to ascertain whether the 
quantity found is normal, or greater or less than normal. For 
this purpose it is necessary to know the average daily or hourly 
quantity of uric acid secreted by healthy people. Numerous 
investigations, especially by Lehmann, Neubauer, and chiefly 
by Kanke, have furnished tolerably accurate information on this 
point. 

"" H. Ranke, Beob. und Versuche liber die Aussclicidurig der Harnsaure 
beim Mensclien, etc., Miinclien, Kaiser, 1858. B. J, Stokvis, Biidragen tot de 
pliysiol. van bet acid, uricum, Ned. Tjidscbr., 1859 (Schmidt's Jabrb., Bd. 109, 
p. 0). Zabelin, Ueber die Umwandlung der Harnsaure im Thierkorper, Annal. 
d. Chem. u. Pbarm. , 1863, Supj)!. ii. , j). 326, et seq. Bartels Untersucbungcn 
iiber die Ursacben einer gesteigerten Harnsaiireausscbeidiing in Krankbeiten 
(Deutscbes Arcbiv f. klin. Med., i., p. 13, et seq.). B. Naunyn u, L. Reiss, 
Ueber Harnsaureausscbeidung (Reicbert's u. DuBois-Raymond's Arcbiv, 1869, 
Heft 3). 

31 



483 SEMIOLOGY OF HUMAN URINE. 

According to these observers tlie average quantity of uric 
acid which an adult individual (male as well as female) passes 
with the urine in twenty-four hours is from 0*3 to 0*8 grm. 
This average quantity, however, differs considerably in differ- 
ent individuals. Also in the same person at different times 
variations occur, which in many individuals are very consider- 
able, in others less. 

The nature of the food appears to exercise the chief influence 
over the quantity of the uric acid excreted. During fasting the 
quantity is diminished very much, it increases rapidly after 
eating, and almost as much after taking non-nitrogenous as ani- 
mal food. (Ranke, "W. Roberts.) 

The relation of the quantity of uric acid to that of urea 
varies considerably (from 1 : 27 to 1 : 80, and indeed in a few 
cases from 1 : 300 and even more). 

Lehmann passed an average of 1*18 grm. of uric acid in 
twenty-four hours, but considered that this was an abnormal 
amount. 

According to Becquerel the daily average quantity amounts 
to 0-49 and 0-56 grm. 

Neubauer found in a large number of observations on two 
healthy persons, that in one the average was 0*28, the maxi- 
mum 0*61, the minimum 0'002. In the second the average for 
twenty-four hours was 0*49, the maximum = 0*67, minimum = 
0-33. 

Ranke, who has made numerous investigations, obtained as 
average numbers for twenty-four hours, in a long series of ob- 
servations on himself, average 0*648, maximum 0*875, minimum 
0-445. In other men, 0-225— 0-654— 0-556— 0*78— average =0*707, 
etc. In two women, the quantity in one was from 0-410 to 
0-456, average ^ 0-429. In the second, from 0-458 to 0-565. 

Regarding the effect of sickness; Ranke found that in inter- 
mittent fever an increased amount of uric acid was excreted 
during the attack. He found, moreover, that the uric acid was 
decidedly increased in leuksemia, a fact which was also observed 
by others ; that it was sometimes diminished in diabetes melli- 
tus, and (as shown by Garrod and Neubauer) always markedly 
diminished in chronic gout (where, according to Garrod, it is 
stored up in the blood). Large doses of sulphate of quinine, 
according to Ranke, diminished the excretion of uric acid. 



QUANTITATIVE CHANGES IN THE URINE. 483 

Bartels found a decided increase of the uric acid, especially in 
proportion to tlie urea, in all of those febrile diseases which are 
accompanied with marked disturbances of the respiratory pro- 
cesses, and he therefore concludes that such an increase is the 
result of a relative respiratory insufficiency, that is, of an in- 
complete oxidation. 

The causes and indications of an increase or diminution of 
the uric acid are, therefore, still somewhat obscure and hypo- 
thetical. Uric acid, like urea, is a product of the body, and in 
fact of the metamorphosis of the nitrogenous constituents. In 
so far it has the same indication as urea. But uric acid stands 
a step higher on the ladder of retrograde metamorphosis than 
urea; the latter may be formed from uric acid by oxidation. 
Therefore uric acid is often regarded as imperfectly oxidized 
urea, and it has been thought that the increase of the uric acid 
has always occurred at the expense of the urea, wherever, 
through the imperfect supply of oxygen, the decomposed nitro- 
genous elements of the body are incompletely oxidized before 
their removal from the system, and consequently in all diseases 
which are accompanied by disturbances of the respiration. 
This opinion, however, does not agree with the fact that per- 
fectly healthy people also always pass a certain quantity of 
uric acid. Moreover, we find in those diseases in which an in- 
crease of the uric acid is most constantly observed — at the 
height of febrile diseases — that the excretion of urea is always 
increased as well as the uric acid. Uric acid, therefore, is surely 
something more than imperfect urea ; but we must wait for 
future investigations to form further conclusions as to the true 
source of its formation and its actual significance in the econ- 
omy. 

Since the phenomena which occur in animals may serve to 
extend our knowledge of these relations, it is worthy of mention 
that in carnivora confined in cages and whose freedom to move 
about at will is, therefore, removed, the uric acid in the urine 
is increased. In herbivora uric acid is not found at all, but it 
appears in their urine when they are fasting, that is, when they 
live on their own flesh. 

We have already spoken of the significance to the physician 
of uric acid deposited as a sediment within the body in § 107. 



484 SEMIOLOGY OF IIU3IAN UBINE. 

§ 127. Fbee Acids.* 

The quantitative estimation of the free acids in the urine is 
easily and quickly made according to the method given in § 68. 
Only it must be commenced as soon as possible after the urine 
is passed, since the quantity of the free acids is readily changed 
by the occurrence of the acid or alkaline fermentation of the 
urine. 

According to F. Soxhlet,t hoTvever, the titration of the degree 
of acidity of the urine by means of a solution of sodic hydrate 
yields a result which is accurate only within tolerably broad 
limits, since there is no soluble phosphate which has a neutral 
reaction, and since in titrating a. point always occurs in which 
both acid and alkaline reactions are present at the same time. 

Still, these limits of error are not so broad as to set aside the 
usefulness of such analyses, especially for practical purposes, 
when we content ourselves with only drawing conclusions from 
them which are not impaired by those unavoidable errors. (See 
§124) _ _ _ ■ 

Numerous observations of this kind which I conducted partly 
myself and partly had cgirried on under my guidance showed 
that a healthy man passed on an average daily about 2 or 4 grm. 
of acids with the urine, and in an hour about O'lO to 0*20 grm. 
(calculated as oxalic acid). The hourly quantity varies not in- 
considerably according to the time of day, and in four different 
persons on whom investigations were made it was uniformly 
greatest at night, least in the forenoon, and between the two 
during the afternoon. 

The average hourly amount in the urine of the individual on 
whom the greatest number of investigations were made was in 
the night 0*19, forenoon 0'13, afternoon 0*15 grm. 

The quantity of acids in the urine is undoubtedly diminished 

* Th. Eylandt, De acidorum sumptor. vi in urinse acorem, Diss, inaug. , Dor- 
pat, 1854. J. Ch.. Lelimann, Bibl. for Laeger xiii., p. 18 (Schmidt's Jahrb., 
Bd. 108, p. 148). W. Roberts, A contrib. to urology, embracing observations 
on tbe diurnal variations in the acidity of urine, chiefly in relation to food, 
Manchester, 1859. Kliipfel (Hoppe-Seyler, Medic, chem, Untersuchungen, 
Heft 8, p. 412, et seq.). A. Sawicky (Pfliiger's Archiv, 1872, v., p. 285, et seq. 
C. Gaethgens, Zur Frage der Ausscheidung freier Saurc durch den Harn (Cen- 
tralbl. f. d. medic. Wissensch., 1872, p. 833, et seq.). 

f Journ. f. prakt. Chemie, 1872, vi. 



QUANTITATIVE CHANGES IN THE URINE. 485 

by tlie use of caustic alkalies, carbonates or organic salts of the 
alkalies, indeed tliey may entirely disappear after large doses 
of these compounds and the acid reaction of the urine become 
alkaline, as in the formation of carbonate of ammonium by de- 
composition of the urea, as has been repeatedly mentioned. 

On the other hand, the acidity of the urine is increased by 
the internal exhibition of the mineral acids. 

Example. In a young man who had taken large quantities of 
mineral acids (SO3 and 0111) for a long time on account of 
severe haemoptysis, the daily average quantity of acid in the 
urine amounted to 5*4 grm. (an average of six days), and in- 
creased on one day to 7*5 grm. Gaethgens found also in dogs 
into whose stomachs he injected dilute SO,, that the free acids 
of the urine were essentially increased thereby (from 13 to 72), 

The very numerous and careful observations made by W. 
Koberts confirm the statements of B. Jones (see page 375, a) 
that during a period of time, from one to three hours after a 
meal, the secretion of acid by the urine diminishes both abso- 
lutely and in relation to the solid constituents of the urine. 
Not unfrequently, indeed, the urine at this time becomes tem- 
porarily alkaline. Mixed, purely vegetable, and purely animal 
diets have the same action. Roberts ascribes this result of 
taking food, as does also B. Jones, not to the secretion of acid 
gastric juice, but rather to the passage of alkaline salts, or of 
those which will become alkaline, from the food into the blood. 

The greater or less amount of acid passed with the urine de- 
pends probably not only on the greater or less quantity taken, 
but also doubtless upon internal changes of metamorphosis, as 
already indicated in § 96, but not yet proved with certainty. 

According to Kliipfel, the free acid of the urine is very much 
increased by great muscular activity. Sawicky, however, was 
unable to confirm Kliipfel's statements. According to his ex- 
perience, the quantity and quality of the food had more influ- 
ence on the degree of acidity of the urine than rest or work. 

Numerous estimations of the quantity of acid in sick people 
have shown that in most diseases, acute as well as chronic, the 
acid is diminished and almost never increased, except in those 
cases in which large quantities of mineral acids have been 
taken. Yet we find during the height of febrile diseases, espe- 
cially in pneumonia, acute rheumatism, etc., that the percentage 



486 SEMIOLOGY OF HUMAN TTItmE. 

of free acid in the urine is not rarely increased, so that it ap- 
pears more acid than in health ; this evidently depends on the 
diminished quantity of the urine in such cases and its conse- 
quent greater concentration. The diminution of the quantity 
of acid in the urine of the sick doubtless chiefly depends on the 
diminished ingestion of food ; perhaps, also, it is due in part to 
a diminution of the muscular metamorphosis in the sick (see 
page 376, b). The investigations which have been made thus 
far, do not allow of more special conclusions. 

Examples — Male : 

In a patient with pneumonia, the quantity of acid gradually 
increased from to 1*50. The average of eight days amounted 
to 0-5. 

In another patient with pneumonia, who died, the daily quan- 
tity varied between 0*9 and 3*0. The average of four days 
was 1*9. 

In a case of gastric fever, the quantity varied between 0*6 and 
1*6. The average of four days was I'lc 

In a case of acute rheumatism, the quantity for several days 
was 0*7 and 1. 

In a case of chronic bronchial catarrh, the quantity varied 
during eleven days between and 0*8. Average = 0*5. 

Female : 

In a girl with scrofulous glandular swellings it was from 1*6 
to 2*4 The average of four days was 2*0. 

In a woman thirty years of age, suffering from spinal irrita- 
tion, from to 0*8. Average of ^\q days = 0*7. 

In a woman seventy years old, suffering from ascites, the 
result of hepatic disease, from to 3*1. Average of eighteen 
days =r 1*41, etc. 

§ 128. Ammonia.* 

The methods of determining quantitatively the ammonia con- 
tained in the urine have been already described in § 77 and § 78. 

* C. Neubauer, Journ. f. prakt. Chemie, Ixiv., p. 177 and 278. W. Heintz 
and H. Bamberger, Wllrzburger medic. Wocbensclir., Bd. 3, Heft 2 and 3. 
L. Tliiry, Zeitsclir. f. rat. Medic, 1863, p. 166, et seq. A. Ducbek, Wocbenbl. 
d. Zeitscbr, d. k. k. Gesellscb. d. Aerzte zn Wien., 1884, Nr. 51. K. Koppe, 
Ueber Ammoniakausscbeidung durcli die Niereu (Petersburger med. Zeitscbr. 
xiv. 2, 1868). 



QUANTITATIVE CHANGES IN THE URINE. 487 

It appears from tlie investigations of Boussaingault, Heintz, 
and Neubaner, that human urine always contains a small quan- 
tity of ammonia. According to many experiments made by Neu- 
bauer on different individuals, the average quantity passed by 
healthy adult males in twenty-four hours was about 0*7 grm. ; 
the quantity, however, may fall to 0'3, and rise to over 1 gram. 
Koppe also found in normal urine from 042 to 0*45 of ammonia 
per thousand parts; in women somewhat less. The absolute 
quantity in men amounted to 0'8 grm. ; in women, to only 0*5 
or 0*6 grm., in twenty-four hours. 

Since only a few experiments have thus far been made on 
this subject, especially on the urine of sick people, the question 
as to what importance the increase or diminution of ammonia 
in the urine has for the physician can at present be answered 
only very insufficiently and hypothetically. 

Duchek found ammonia always in the freshly passed urine of 
patients suffering from various febrile diseases and in not in- 
considerable quantity, though it did not essentially exceed the 
quantities given above as observed in the urine of healthy peo- 
ple. The quantity of ammonia contained in the urine, more- 
over, appeared to him to increase with the aggravation of the 
symptoms of the disease, and to decrease as convalescence oc- 
curred. Koppe found the excretion of ammonia was increased 
in infectious diseases (1*3 to 1*5 grm. in twenty-four hours), 
and in the florescent stage of typhus, where it is increased with 
the temperature of the body. 

The following considerations may serve as a hint, and at the 
same time as an incentive to further investigations : 

The ammonia in the urine is evidently derived from two 
quite different sources : 

1. It is derived from the food, from the drink, and from 
the respired air which contains more or less ammonia. Still, 
generally speaking, the amount of ammonia in these ingesta is 
but small, and consequently the quantity removed from the 
system by the urine is inconsiderable as a rule, less than J 
grm. in twenty-four hours. Under certain circumstances an 
unusually large quantity of ammonia maybe taken into the sys- 
tem from without in health, as when we remain in an atmo- 
sphere filled with tobacco smoke, or eat certain food which 
contains much ammonia, such as radishes, etc. ; in the sick, 



488 SEMIOLOGY OF HUMAN URINE. 

when, preparations of ammonia are given as medicines, such 
as the carbonate or chloride of ammonium, etc. Neubauer has 
shown that the greatest part of the chloride of ammonium in- 
gested is eliminated again by the urine. In all cases in which 
the daily quantity of ammonia in the urine exceeds 1 grm. the 
physician should ascertain whether the excess depends upon 
one or several of these causes. 

2. Without doubt ammonia may also be produced within the 
body by pathological processes. We know with certainty that 
urea may be decomposed into carbonate of ammonium, and one 
of the theories of ursemia is founded upon this dangerous pro- 
cess, that the urea retained in the system undergoes this change 
into carbonate of ammonium. The facility with which ammo- 
nia develops from all nitrogenous animal compounds, especially 
from the blood, the so-called extractive matters, etc., outside of 
the body, when a slight degree of decomposition has set in, 
allows us to conclude that in the pathological processes which 
we call putrid and septic, conditions of decomposition, such a 
development of ammonia has already taken place within the liv- 
ing body. Therefore, the detection of an increased separation 
of ammonia from the system is of great weight in the diagnosis 
of such conditions of disease (ammongemia). The ammonia 
may be separated not only by the urine, but also in other ways, 
as by the intestine and the lungs, but its quantitative estima- 
tion in the urine is at present our simplest and surest guide. 

Great care, however, is necessary in the investigation of all 
such cases, since under these circumstances the urea of the 
urine has a great tendency to decompose (which, as Neubauer 
has shown, does not happen in normal urine), and it is, there- 
fore, very difficult to determine how much of the ammonia 
present in the urine was present when it was first secreted, and 
how much has been formed by the subsequent decomposition 
of urea in the bladder or outside of the body. In order to avoid 
this source of error as much as possible, I would advise in all 
such cases : 

1. To subject the urine to examination as soon as possible 
after its secretion by the kidneys, by introducing a catheter to 
draw off all of the urine present in the bladder, and then to 
subject that which drops from the catheter subsequently to an 
examination. 



QUANTITATIVE CHANGES IN THE URINE. 489 

2. To free this urine from coloring matter, extractive matter, 
mucus, etc, by the addition of acetate and basic acetate of lead 
solutions, as described on page 308, so as to guard against 
further decomposition as much as possible. 

Sometimes the urine contains sulphide of ammonium. Betz 
considers that in such cases it comes from the intestine, from 
which it is absorbed into the blood, and there causes danger- 
ous symptoms of disease (hydrothion-ammonaemia). (See page 
113.) The acceptance of this origin, however, requires further 
proof, since the intestine, even in perfectly healthy persons, very 
often contains sulphuretted hydrogen without showing any re- 
sults of the action of this poisonous gas on the blood. 

§ 129. Chloeine and Chlobide of Sodium."^ 

For the methods of estimating the amount of chlorine and 
common salt in the urine, see § ^Q. 

It is immaterial whether the result of the estimation is reck- 
oned as chlorine or chloride of sodium, although it is certain 
that in many cases all of the chlorine in the urine is not com- 
bined with sodium. Therefore care must be taken not to con- 
found the figures indicating chlorine with those Avhicli indicate 
chloride of sodium, which occasionally has happened, and has 
led to error, since many writers calculate their results as chlo- 
rine, and others as chloride of sodium. 

The starting point for deciding whether the elimination of 
chlorine with the urine is increased or diminished is the knowl- 
edge of the average daily elimination of chlorine in health. 
Hegar has reported a series of very careful examinations of the 
daily and hourly elimination of chlorine with the urine in seven 
young healthy men. The average daily amount in the urine 
varied with the individual, between 7*4 and 13 '9 grm. There- 
fore the average daily amount of chlorine passed with the urine 
by an adult man is about 10 grm. (=16*5 grm. NaCl), or hourly 
about 0*44 grm. 01 (0*73 ]^aCl). These figures are, however, 

* Alfr. Hegar, Ueber die Auscheidung der Clilorverbindungen durcli den 
Harn. Giessen, 1852. F. Howitz, Hospitals Meddelelser : andere Roekke, Bd. 
1, p. 64, et seq. ; Schmidt's Jalirb., Bd. 95, p. 282, et seq. E. Ph. Hinkelbein, 
Ueber den Uebergang des Chlornatriums in den Ham., Inaug. Diss., Marburg, 

1859. 



490 SEMIOLOGY OF HUMAN URINE. 

probably somewliat too liigli, since the individuals taken for 
tlie examination were mostly students who were strong, ate 
food with much salt, and drank much. A somewhat lower 
figure would be more nearly correct for the majority of adults, 
about 6-8 grm. CI {=: 10-13 grm. NaCl) daily, and 0-25-0-33 grm. 
CI (=0*41-0 '54 grm. NaCl) hourly. In women and children the 
amount of chlorine eliminated is still less. 

Bischoff found as the mean daily amount of chlorine in the 
urine of a well-nourished adult man, 8'7 grm., of a woman 
43 years old, 5*5 grm., of a girl 18 years old, 4*5 grm., of a 
boy 16 years old, 5*3 grm., and in that of a boy of 3 years, 
0*8 grm. Becquerel found only 0*66 grm. CI in the ignited 
residue of the daily urine of a healthy person, an estimate, 
like all others obtained in the same way, naturally of no 
yalue. 

But very considerable variations in the amount of chlorine 
eliminated daily and hourly may occur, not only in different 
individuals, but also in the same person under conditions 
of health. This follows partly a certain rule. Thus, in all 
healthy j)ersons examined, the maximum chlorine elimination 
occurs in the afternoon, and the minimum at night. 

Hegar found as the mean hourly elimination in eight indi- 
viduals : afternoon, 0*57 ; night, 0*28 ; forenoon, 0*48 grm. The 
same author found in the same individual variations in the 
hourly elimination from 0'20 to 1*32 grm., so that the hourly 
maximum exceeded the minimum more than sixfold. 

The following are doubtless the causes which produce an in- 
crease or a diminution in the chlorine elimination in healthy 
persons : 

1. The taking into the organism of a greater or less amount 
of chlorine, esj^ecially of common salt, which we eat with our 
food, has without doubt the greatest influence. Persons who 
eat much salt with their food have a greater average elimina- 
tion of chlorine, and a temporarily increased ingestion of chlo- 
rine results, as a rule, in a temporary increase in the elimina- 
tion. That the greatest hourly chlorine elimination in all 
persons examined here occurs during the afternoon and even- 
ing hours, depends, without doubt, chiefly upon the fact that 
all of these persons eat the greatest amount of salt with their 
principal meal at noon, a part being eliminated soon after its 



QUANTITATIVE CHANGES IN THE URINE. 491 

passage into the blood. But also direct experience shows that 
after the increased ingestion of chlorine there is an increased 
elimination with the urine and vice versa. 

Falck eliminated with the urine daily : 1. When eating food 
well salted — on the first day, 6*0 grm. CI ; on the second, 7 '8 
grm ; on the sixth day, 10-3 grm. 2. When eating food not 
salted — on the first day, 2*5 grm. CI ; on the second, 1'6 grm., 
and on the third day, 0'9 grm. 

Several persons here took, for the purpose of experiment, 
common salt in non-purgative doses. In all cases the hourly 
elimination with the urine was increased ; it rose from 0*4 grm. 
to I'O, and even to 1*8 grm. In some the chlorine which was 
absorbed into the blood was again separated from it in large 
amount and quickly, but in others in smaller quantity and 
more slowly. 

In experiments which Stokvis undertook, the amount of chlo- 
rine in the urine diminished rapidly with the diminution of the 
amount ingested, and rose again gradually when more salt was 
eaten. 

2. But the amount of chlorine eliminated with the urine de- 
pends not only upon the amount ingested, but may be increased 
or diminished by other circumstances, and even by conditions 
which lie within the organism itself. In all of the persons ex- 
amined by Hegar, the hourly elimination in the forenoon hours 
(0*48 grm.) was much greater than during the night (0*28 grm.), 
although one of these persons was accustomed to eat a meal of 
well-salted food in the evening, and then take nothing but a 
glass of water until the next noon, and the others also ate food 
rich in salt in the evening, but in the morning only food con- 
taining but little salt (coffee and rolls) ; so that in all of these 
cases there must have been other causes which diminished the 
power of the kidneys to eliminate chlorine during the night 
and increased it during the forenoon. Without doubt these 
causes are, on the one hand, the physical and mental quiet 
during sleep, and on the other, the greater activity of metamor- 
phosis during the morning, causes which, as has been already 
shown, exert an analogous influence upon the amount of the 
urine and of the urea. An exceptional case, agreeing with this 
theory, occurred in one of the persons examined by Hegar, who 
was accustomed to strenuous mental exertion during the greater 



492 SEMIOLOGY OF HUMAN URINE. 

part of tlie niglit, in wliom tlie mean hourly amount of chlorine 
in the night urine (0'47 grm.) exceeded that in the morning 
urine (0*44 grm.). I have also frequently observed myself that 
the elimination of chlorine was temporarily considerably in- 
creased by an increase of physical and mental labor. Agreeing 
with this also, the observation has been made that drinking a 
large amount of water, which excites the activity of the kidney 
and increases not only the amount of urine but also the amount 
of urea eliminated, as a rule, causes also a temporary increase 
in the amount of chlorine eliminated, followed usually by a 
diminution or lessening of the activity. 

Example. H. drank in the evening four glasses of water. 
The hourly elimination of chlorine, which averaged in this per- 
son only 0*13 grm. during the night, rose during the next hours 
to 0*60 grm., then fell to 0*12, and later to O'lO grm., and rose 
again in the morning without anything more having been eaten 
by increased metamorphosis (riding) to 0*51 grm. 

H. y. drank in the afternoon four glasses of water. The 
hourly chlorine elimination thereupon increased during the 
evening hours to 1-89 grm., and averaged during the night 0*57 
grm. (instead of 0*38 grm.). In the morning two glasses more 
of water were taken, in spite of which the amount remained 
during the whole day below the normal (0*42 grm.), and even 
fell during the night to 0*014 grm. ( ! ), in the morning rose again 
somewhat (to 0"22 grm.), but then fell once more (to 0*18 grm.), 
notwithstanding that bread and butter with a large amount of 
salt was eaten. 

From these results it follows without doubt that the amount 
of chlorine eliminated depends not only upon the amount in- 
gested, but that it is influenced much more by other causes, es- 
pecially those which act generally upon the activity of the kid- 
neys, producing an increase or diminution in the amount of 
urine. But it is very difficult to estimate accurately the influ- 
ence of these conditions upon the elimination of chlorine gen- 
erally, and particularly in any given case. In order to do this 
we must give the individual chosen for the investigation a diet 
absolutely free from chlorine, which would, however, certainly 
disturb the purity and usefulness of the results obtained, or we 
must take the greatest care to estimate accurately the amount 
of chlorine in all of the food taken while the investigation lasts, 



QUANTITATIVE CHANGES IN THE VRINE. 493 

as lias been done by Barral in some cases in his careful investi- 
gations." 

We will now turn to the consideration of the elimination of 
chlorine in disease. In this subject I have a very large number 
of experiments, part of which I have performed myself and 
part have superintended. The results are chiefly as follows : 

1. In all acute febrile diseases the amount of chlorine elimi- 
nated with the urine diminishes rapidly, frequently sinking to 
the minimum, almost to complete disappearance, so that some- 
times it amounts to scarcely the one-hundredth part of the nor- 
mal. With commencing recovery it increases, and during con- 
valescence sometimes exceeds the normal. Its curve usually 
runs parallel with that of the amount of urine, for the most 
part, however, in the opposite direction to that of the specific 
gravity and the coloring matters, and at the beginning to that 
of the urea, but during convalescence frequently parallel with 
that of the urea. 

Example. In the case of a man with severe pleuropneumonia 
the chlorine diminished rapidly, amounting on the third day 
after the commencement of the disease to 0'6 grm. daily, on the 
next day to 0*3 grm., and on the following to almost 0, from 
which time it increased continuously with the decrease of the 
disease and the increase of the appetite, with tolerable regu- 
larity, until the normal was reached (0'4 — 1*8 — 2*6 — 5'5 — 9*0 
grm.). From this time the curve became irregular, and some- 
times exceeded the normal (lO'T— 13-5— 9-7— 11-9— 15-9— lO'S 
grm.). 

In a typhoid-fever patient it fell quickly to a minimum, re- 
maining for several days almost at 0. Then it increased with 
advancing recovery gradually, with variations, until it reached 
the normal. 

In a woman with acute rheumatism and pericarditis it fell 
during the acme to I'O grm., and rose gradually during con- 
valescence to 6'3 grm. 

In a young man with severe febrile bronchial catarrh it fell 
quickly to 0*8 grm., and then rose during five days to 10*6 grm. 

In an older man also with febrile bronchial catarrh it fell to 



* J. A. Barral, Statique chimique des animaux, appliquee specialement ^ la 
question du sel, Paris, 1850. 



494 SEMIOLOGY OF HUMAN- VRINE. 

VI grm., but tlien rose during convalescence, when an abun- 
dant amount of nourishment was taken, to the enormous height 
of 20*5 grm. 

In a man with exudative pleurisy it diminished to a mere 
trace, and then rose again with some variations, without, how- 
ever, reaching a very high figure (3"0 — 3*2 — d'S — 1'6 — 4-0 — 4:'5 
— 4*9 — 4*6 grm.). 

The cause of this very great diminution in the amount of 
chlorine eliminated in all acute diseases is, without doubt, 
chiefly the diminution of the appetite and the meagre diet, poor 
in salt, taken by such patients ; the separation of chlorine from 
the blood by other channels (watery diarrhoea, serous exuda- 
tions) sometimes causes it. By all of these conditions the 
amount of chlorine in the blood is certainly diminished, and 
since, as we see in health, the excess of chlorine in the blood is 
preferably separated by the kidneys, it is very probable that 
the amount of chlorine in the urine is diminished. 

The amount of chlorine eliminated with the urine is also 
directly dependent upon the amount of urine, and the circum- 
stance, that this is always considerably diminished in all acute 
febrile diseases, probably diminishes also the amount of chlo- 
rine compounds eliminated. 

Since the above statements concerning the elimination of 
chlorine with the urine in disease, based upon numerous in- 
vestigations of my own, were published, several works upon 
this subject have appeared, such as that of Howitz and Hin- 
kelbein mentioned above, and those of Alfr. Yogel, Moos, and 
Brattler mentioned in connection with urea, which also dealt 
with the elimination of chlorine with the urine. They confirm, 
in the main, the above statements, and especially that it is 
not in single forms of disease only that the diminution in the 
amount of chlorine is observed, for example, in pneumonia, but 
in the luliole class of the above-mentioned diseases, so that the 
diminution or the disappearance of the chlorine compounds 
from the urine cannot, as some state, be used for the purpose 
of making a differential diagnosis, of pneumonia, for example. 
My results have been confirmed by those of Howitz and Fel. 
Hoppe^ in this respect also — that this diminution of the chlo- 

* Deutsche Kliuik, 1858, No. 53. 



QUANTITATIVE CHANGES IN THE URINE. 495 

rine is particularly dependent upon the diminished ingestion 
of chlorine (naturally together with the other causes mentioned 
above). 

An exception to this rule, which otherwise applies to all 
acute febrile diseases, is intermittent fever. In this disease the 
elimination of chlorine with the urine appears usually to be in- 
creased, in many cases to a very great extent, during the par- 
oxysm, sometimes shortly after it, and more rarely shortly 
before it. 

Example. W. K. suffered with tertiary intermittent. Shortly 
before the attack the hourly amount of NaCl eliminated with 
the urine was 0*07 grm., during the paroxysm it rose to 0'62 
grm., then fell to 0-39 grm., and in the following interval to 0'17 
grm. During the next paroxysm it increased again to 0*93 grm. 
and fell again during the interval to 0*04 grm. 

A. S. Tertiary intermittent. The hourly amount of chloride 
of sodium was 0*05 grm. before the paroxysm, rose to 2'5 grm. (!) 
during it, fell again to 0*12, and then rose again gradually to the 
normal, since there were no more attacks. 

A. C. Tertiary intermittent. The hourly elimination of chlo- 
ride of sodium amounted to 0*42 grm. before the attack, rose to 
1*30 grm. during it, and then fell to 0*15 grm. It rose again 
toward the end of the interval, reached its maximum of 0*63 
grm. shortly before the beginning of the fever, and then fell to 
0-08 grm. 

The same rule naturally applies to women. Auguste.S. 
suffered from tertiary intermittent. The hourly elimination of 
chloride of sodium amounted to 0*15 grm. shortly before the 
attack, during the paroxysm it reached the enormous height of 
4*12 grm., and fell again after the paroxysm to 0*06 grm. 

The average daily elimination of chlorine in intermittent 
fever is, however, somewhat less than normal, but it does not 
for any length of time undergo the considerable diminution 
which is observed in other acute diseases ; this is due to the 
fact that intermittent-fever patients frequently have during the 
interval a good appetite and eat food with the ordinary amount 
of salt. The increased elimination during the paroxysm is pro- 
bably due to the increased blood pressure in the Malpighian 
bodies of the kidneys during the chilly stage. A diminished 
separation of chloride of sodium from the blood, which has be- 



496 SEMIOLOGY OF HUMAN UBINE. 

come poor in salt, tlien naturally follows the increased elimina- 
tion. 

2. In cJironic diseases the elimination of chlorine is subject to 
great variation. As a rule it is diminished, corresponding to 
the diminished metamorphosis and ingestion of food by such 
patients, but in individual cases it is, on the contrary, increased. 
Some groups of diseases belonging under this head are of 
special interest in this respect and deserve a more accurate 
consideration. 

The chlorine apppears to be increased in diabetes insipidus, 
sometimes temporarily, sometimes for a long time together 
with an increase in the amount of urine and of the solid consti- 
tuents generally. In one case of this kind I found the elimina- 
tion of chlorine with the urine increased for a long time, so 
much that on one day the enormous amount of 29 grm. was 
reached. 

In dropsy at the time when the elimination of urine is sup- 
pressed, a part of the salt eaten is held back in the body : it 
transudes with the dropsical fluid into the tissues. With the 
appearance of diuresis the elimination of chlorine increases to- 
gether with the amount of urine, and then sometimes reaches 
an enormous amount. Thus, in one case, such a patient passed 
on three successive days 33 ( = 55 grm. NaCl), 28, and 21 grm. 
of chlorine, and in another the elimination of chlorine rose 
within twenty-four hours, on account of the influence of a decoc- 
tio^i of digitalis, from 4 grm. to 27, without the ingestion of 
chlorine being in the slightest increased. The same process 
which is injurious in the first class of cases, diabetes, by with- 
drawing substances from the economy which are necessary, is 
beneficial in the latter class, dropsy, by separating the super- 
fluous material. While a certain amount of chloride of sodium 
appears to be necessary to the organism, partly for many secre- 
tions, partly for the purposes of intermediate metamorphosis, 
secretion of the gastric juice, the bile, and for the formation 
of many tissues (especially cartilage?), nevertheless an excess 
of it may be injurious, namely, by preventing the formation of 
the blood and by displacing albumen.'^'' 

■" Concerning this last property I liave already given a detailed treatise in tlie 
Handbucli der spec. Pathologie und Therapie, published under R. Vircliow's 
revision, Bd. 1, page 404, et seq., and I must hero refer to tliat treatise. 



QUANTITATIVE CHANGES IN THE URINE. 497 

A quantitative estimation of the amount of chlorine elimi- 
nated with the urine may in the present state of our knowledge 
give the practising physician information upon the following 
points : 

In all acute diseases a progressive diminution of the chlorine 
shows an increase, and progressive increase of the chlorine, a 
diminution of the disease. If the chlorine falls to a minimum 
(below 0*5 grm. daily), the conclusion that there is a consider- 
able intensity of the disease, a complete failure of the appetite, 
or, under certain circumstances, a previous abundant watery 
diarrhoea or moderate serous exudation is warranted. If the 
chlorine increases again in the urine we may, from its amount, 
draw a tolerably accurate inference as to the condition of the 
appetite and digestion of the patient. In all of these cases 
a very approximate estimation of the amount of chlorine is 
usually sufficient, and an error of 50 or 60 per cent, is of no 
importance, especially in cases where the elimination of chlo- 
rine is very slight. 

In chronic diseases the amount of chlorine is of importance 
to the physician, since it is a tolerably accurate measure of the 
digestive power of the patient. An abundant amount of chlorine 
(6-10 grm. daily) permits us to infer that digestion is good, a 
small amount (below 5 grm.) shows a weak digestion, providing 
that no large amount of chlorine is separated by other channels, 
as, for example, by abundant watery dejections, or any other 
moderate exudation, or that the diet of the patient has uninten- 
tionally been so chosen that a very small amount of chlorine is 
ingested. A very much increased chlorine elimination (more 
than 15-20 grm.) indicates diabetes insipidus, provided that 
there has not been an increased ingestion with food or drugs. 
Only in hydrsemia and dropsy is it a good sign. The considera- 
tion of the other urinary constituents serves often to strengthen 
or to modify the inferences drawn from the amount of chlorine 

alone. 

§ 130. SuLPHUEic Acid.* 

The methods for determining quantitatively the amount of 

* G. Gruner, Die Anssclieidung der Scliwef elsaure durcli den Ham, Giesscn, 
1853. Wald. Clare, Experimenta de excretione acidi sulfuric! per urinam, Dor- 
pat, 1854 P. Sick, Vers, iibcr die Abhangigkeit des Schwefelsauregelialts des 
Urines von der Scliwef elsaurezufulir, Inaug, Ablidlg., Tiibingen, 1859. 
32 



498 SEMIOLOGY OF HUMAN URINE. 

sulphuric acid in the urine have been already described in § 69. 
Both the gravimetric and the volumetric methods, when they 
are carefully performed, give very accurate results. If it is de- 
sired to obtain the result very quickly, the volumetric method 
should be used without boiling, since this operation is usually 
inconvenient for the physician. But the result is then less ac- 
curate, and the error may reach 10 per cent. An approximate 
estimation, which will not accurately give the amount of sul- 
phuric acid contained in the urine, but will only show whether 
it exceeds or falls below a certain point, may be performed still 
more quickly, and is sufficient for most purposes of the phy- 
sician. An example will explain the principle and the per- 
formance. 

We will take the case in which the physician wishes to know 
whether the elimination of sulphuric acid with the urine of a 
patient is considerably increased or diminished. The average 
noi^mal amount of sulphuric acid in the urine daily is about 2 
grm. The patient whose urine is to bo examined has passed 
2,000 cc. in the twenty-four hours. If this contains the normal 
amount of 2 grm.^ then 100 cc. of it, which are taken for analy- 
sis, will contain 0*10 grm. of SO;;. To this 100 cc. is now added, 
after it has been acidulated, an amount of chloride of barium 
equivalent to 0*05 grm. SO3, and filtered. If the filtrate is not 
rendered turbid by more chloride of barium, we know that 
the patient is secreting less than 1 grm. of SO3 in twenty-four 
hours, and, therefore, that the elimination of sulphuric acid is 
considerably diminished in his case. If the filtrate is rendered 
turbid, however, by the addition of more chloride of barium, 
enough more must be added to correspond to 0*05 grm. of SO^. 
If then, after filtering, a turbidity is caused by the addition of 
chloride of barium, the amount of sulphuric acid in the urine 
exceeds the normal. Such approximate estimations, which are 
entirely sufficient for many practical purposes, may be per- 
formed in a few minutes, and in a clinic, directly at the bed- 
side. Even in cases in which a more accurate estimation is de- 
sirable, they may profitably be performed as a preliminary to a 
more careful analysis. 

The average amount of sulphuric acid eliminated with the 
urine in health has been established with tolerable certainty by 
different observations in various places. Thus Gruner, who 



QUA2fTITATIVB CUANOES IN THE UBINE. 499 

made liis investigations in Giessen upon seven young men, 
found as the average of the daily elimination 2*094 grm. Of 
these seven persons the average in those who passed the least 
sulphuric acid was 1*509 grm., and in those who passed the 
most was 2*485 grm. These figures, reckoned for 100 kilogr. 
weight of the person, give as the average 3*19, minimum 0*85, 
maximum 3*73 ; reckoned for 100 ctm. height of the person, 
give as the average 1*18, minimum 1*04, maximum 1*35. Clare 
found that the average daily elimination for 15 days in a young 
man in Dorpat was 2*288 grm., minimum 1*858, maximum 2*973. 
Neubauer found in one of two men living in Wiesbaden as the 
daily average (for 17 days) 2*48 grm., minimum 1*90, maximum 
3*21 grm. In the other the average for 22 days was 2*27, mini- 
mum 1*70, maximum 3*20 grm. Sick found as the average in 
his own case 2*46 grm. Weidner, 2*1 grm. Therefore the aver- 
age daily elimination of sulphuric acid with the urine in healthy, 
well-nourished men varies between 1*50 and 2*50 grm. Gruner 
and I have made direct experiments upon the hourly elimina- 
tion of sulphuric acid in health and upon its variations. From 
these it follows that the general hourly average is about 0*090 
grm., that in the afternoon is 0*108 grm., in the night 0*070 grm., 
and in the forenoon 0*063 grm. From this the general rule fol- 
lows that the elimination of sulphuric acid is most abundant a 
few hours after the principal meal, and then falls constantly 
until the time of the principal meal on the following day, after 
which it begins to rise again. But with different individuals 
the elimination of the sulphuric acid taken into the body with 
the food takes place with more or less energy, more quickly or 
more slowly, so that the sulphuric acid curve becomes more or 
less steep. But the variations in the hourly elimination of 
sulphuric acid are very considerable in the same person. Thus 
one person evacuated in one hour a maximum of 0*165 grm., 
and at another time in two hours an amount so small that it 
could not be estimated, at the most, therefore, a couple of milli- 
grams. In another person the hourly maximum was 0*317 grm., 
and immediately afterward only 0*016 grm. were passed per 
hour. 

As to the causes which influence an increase or diminution of 
the sulphuric acid elimination in health, the investigations 
have been quite numerous. 



500 SEMIOLOGY OF HUMAN UBINE. 

It follows from the above reported rate of the hourly elimina- 
tion of sulphuric acid, that it depends to an important extent 
upon the amount of sulphuric acid or other sulphur compound, 
which is converted within the organism into sulphuric acid, 
taken into the body with the food. But it is also proven by 
numerous experiments, that sulphur compounds which are taken 
into the body in other ways, as for example as drugs, cause an 
increase of the SO3 elimination. The investigations hitherto 
made in this respect teach us the following points : 

1. The elimination of sulphuric acid is increased by the in- 
gestion of sulphuric acid, sulphates, and other sulphur com- 
pounds whose sulphur may be oxidized within the body to 
sulphuric acid. 

Examples. In the case of a patient in my clinic, who took SO3 
for a long time on account of haemoptysis, the daily sulphuric 
acid elimination was increased from 1*2 grm. to 3'0 and even 
3-28 grm. 

Also in a case of SO^ poisoning, the amount of it in the urine 
during the first 24 hours was much increased. (Mannkopff.) 

In several experiments the hourly elimination of sulphuric 
acid was much increased by taking sulphate of sodium. Thus in 
one it was increased from 0*049 grm. to 0*122 — 0*176 — 0*145 and 
0-220 grm., and in another from 0*041 to 0*138—0*122 and 0*164 
grm. This increase continued sometimes for a longer and 
sometimes for a shorter time, that is, the sulphuric acid ingested 
was separated from the body in some cases quickly and in some 
more slowly. (Gruner.) 

According to Krause ^'' the internal use of sulphur increases 
the amount of sulphuric acid in the urine ; it is also increased, 
according to the experiments of Boecker and Clare, after large 
doses of sulphur auratum antimonii (golden sulphur). 

It follows from the experiments of Sick that small doses of 
sulphate of sodium taken internally are completely absorbed 
and eliminated with the urine, while only a part of large doses 
appears again in the urine — which would be expected on ac- 
count of the cathartic action of large doses of Glauber's salt 
(sulphate of sodium). 

C. Gaethgens t found also that in dogs after the injection of 

■^A. Krause, De transitu sulfuris in urinam, Dorpati, 1853. 
f Centralbl. 1 d. medic. Wissenscli. , 1872, p. 833, ct seq. 



QUANTITATIVE CHANGES IN THE URINE. 501 

dilute sulphuric acid into the stomach its amount in the urine 
was considerably increased (from 2*7 to 7'1 grm.). 

2. The sulphuric acid elimination is very decidedly increased 
after the abundant ingestion of meat, which is probably due 
to the separation during digestion of the sulphur which is in 
combination with the protein substances in the meat, and its 
gradual oxidation in the blood to sulphuric acid, in which form 
it is eliminated with the urine. This increase of the SO3 in 
the urine after eating meat sometimes appears quickly, a few 
hours after eating, and sometimes not for a long time, 12-24 
hours, a difference which is probably due to the greater or less 
rapidity of digestion. On the other hand, the sulphuric acid 
elimination is diminished by a predominance of vegetable food. 

Examples. A person who had eaten in the evening a very 
hearty supper consisting chiefly of meat, evacuated from 12 
o'clock at midnight to 9 o'clock in the morning 0*50 grm. of 
SO3 per hour instead of O'lO grm., and during the next 24 hours 
it amounted to the enormous sum of 7*3 grm. (!) instead of the 
daily average of 2*02 grm. 

Several persons, whose metamorphosis I investigated, con- 
stantly eliminated more SO3 when they had eaten meat on the 
previous evening, and less when they had eaten no meat but 
only bread and butter, rice, and similar substances. 

Very instructive in this respect is a series of experiments 
which Clare made upon himself. During three days he took 
only a meat diet, and in this time evacuated, on the first day 
2*094, on the second 5-130, and on the third 3*868 grm. of SOc. 
Then for two days he ate ordinary food and evacuated on the 
first day 3'592, and on the second 2-262 grm. of SO;.. On the 
three following days he lived upon an exclusively vegetable 
diet, when the amount of SO3 was on the first day 2*262, on the 
second 1*394, and on the third 1*022 grm. ; on the two follow- 
ing days with ordinary diet it was 1*979 and 2*859 grm. It is 
plainly seen here that the increase of the SO3 caused by the 
meat diet first appeared on the second day, but extended over 
into the first day of the ordinary diet ; in like manner the di- 
minution of the SO3 caused by the vegetable diet first appeared 
on the second day and extended over into the first day of the 
ordinary diet. Therefore, in these cases the action appeared 
later than in those which were observed by me, probably on 



502 SEMIOLOGY OF HUMAN URINE. 

account of individual predisposition, and for tliis reason proba- 
bly another experiment of Clare, in wliicli lie ate on alternate 
days a meat and vegetable diet, gave no positive result. 

Does tlie amount of sulphuric acid eliminated with the urine 
always depend entirely upon the amount ingested, or are there, 
as with common salt, cases in which the elimination of this 
substance is increased or diminished by other conditions, so 
that the system gives up a portion of its usual, fixed, normal 
amount of sulphur or sulphuric acid, whereby it becomes 
poorer in this constituent than usual, or, on the contrary, holds 
back a portion of the sulphuric acid obtained from without, 
and thereby becomes richer in this constituent than usual? 
This question cannot yet be answered with certainty. Gru- 
ner and Clare have endeavored to determine by experiments 
whether rest or strenuous exertion exerted any influence upon 
the SO3 elimination. None of their experiments gave a satis- 
factory result. Drinking a large amount of water, which de- 
cidedly increases the secretion of urea and chloride of sodium, 
has no marked influence upon that of sulphuric acid. But we 
are not yet warranted in concluding from these experiments 
that the SO3 elimination is not affected by such influences : it 
may have been very slight, or have been prevented in these ex- 
periments by opposing influences. The fact mentioned above, 
that the sulphates or sulphur constituents of meat which is 
eaten are eliminated rapidly by some persons and more slowly 
by others, renders it extremely probable that there exist still 
other considerations lying within the organism itself, which 
regulate the SO3 elimination, and that this power varies in dif- 
ferent persons and in the same person under different circum- 
stances. Also the experience often met with, that sulphates 
taken for a long time in digestible doses exert a decidedly dif- 
ferent action, is to my mind a proof that under certain circum- 
stances an amount of them greater than the normal may be 
retained within the organism. A definite answer to this ques- 
tion can only be obtained by either accurately estimating the 
amount of sulphur and sulphuric acid in the blood and other 
parts of the body under different circumstances, or by simul- 
taneously accurately determining quantitatively the amount of 
sulphuric acid eliminated from the body and that taken into it. 
Both of these requirements are so difiicult to fulfil, that this 



QUANTITATIVE CHANGES IN THE TIRINE. 503 

question will probably remain unanswered for a long time to 
come. 

As to the sulphuric acid elimination in disease I have made 
quite a number of investigations, without as yet having arrived 
at any very valuable result. In most acute febrile diseases I 
found the SO3 very much diminished, which was without doubt 
due to the scanty diet and the predominance of vegetable food 
in such cases. 

Examples. A man suffering with buccal diphtheria with vio- 
lent fever evacuated in the twenty-four hours only 0*5 grm. of 
SO;;. A patient with catarrhal fever 0*29 and 0*38 grm. One 
with pleurisy 0*63 grm. An exception occurred, however, in 
three cases of severe pneumonia, in which the sulphuric acid 
was partly slightly diminished and partly considerably in- 
creased. One of these patients, who was treated with large 
doses of digitalis, evacuated 2-4— 3-1— 2-9— 5-7— 4-3— 1-8— 1 1— 
1'6— 2*7 grm. Of the other two, in whom the pneumonia rapidly 
proved fatal, one eliminated 2*9 and 1*4 grm., and the other on 
the day of death 4*4 grm. 

A girl with severe rheumatic fever eliminated at the acme of 
the disease 0*8 grm. One with facial erysipelas passed 048 grm. 

In chronic diseases also the sulphuric acid elimination was 
very slight in many cases, in others somewhat greater, but still 
considerably below the normal. In dropsy, at the time when, 
on account of diuresis, the chlorine elimination is so enormously 
increased, the sulphuric acid, as a rule, remains below the nor- 
mal. In chronic diseases the SO3 was found to be increased 
almost only after the use of sulphuric acid or sulphates, and in 
diabetes where an abundant meat diet was eaten. 

Examples. A patient with icterus passed 1'4 grm. of SO., 
and one with rheumatism of the neck 1*11 grm. A patient with 
emphysema of the lungs 1*2 grm., one with amenorrhoea 0*5 
grm., a girl with leucorrhoea 0*7 grm., and a patient with habi- 
tual hypermenorrhoea '97-1*1 grm. A dropsical patient, after 
diuresis had commenced, passed in twenty-four hours 33 grm. of 
chlorine with the urine, but in the same time only 1 grm. of 
SO., and on the following day when he passed 28 grm. of chlo- 
rine only 0*5 grm. of SO^. A patient who "had taken SO3 elimi- 
nated in twenty-four hours over 3 grm., and one with diabetes 
insipidus up to 5*2 grm. of SO3. 



501 SEMIOLOGY OF HUMAN URINE. 

According to Bence Jones, in those diseases in wliich the 
muscular system is especially attacked, as in chorea, also in 
diseases of the brain, both functional, as in delirium, and or- 
ganic, as in inflammation of the brain, the sulphates in the 
urine should be considerably increased. Heller claimed the 
same for inflammatory diseases, while, according to him, the 
SO3 should be diminished in chlorosis, the neuroses, and in 
chronic renal and spinal affections. The methods, however, 
which both of these investigators used were not sufficient to 
decide this difficult question. Single observations which Leh- 
man and Gruner made are not favorable to that view. My own 
observations in those diseases have not been sufficiently numer- 
ous to enable me to draw any definite conclusions either for or 
against them ; the three cases of pneumonia reported above 
appear at all events to favor the view that in many inflamma- 
tory diseases the SO3 increases. 

The physician can, in the present state of our knowledge, 
draw the following conclusions from an increase or diminution 
of the sulphuric acid in the urine : 

1. A considerable diminution of the SO3 indicates that the 
patient has eaten very little animal food, or only vegetable 
food ; 

2. An habitual, abundant sulphuric acid elimination in con- 
nection with a large amount of urea, indicates a preponderance 
of animal food. A temporary and considerable increase allows 
us to conclude that sulphur, sulphuric acid, sulphates, or large 
quantities of meat have been eaten ; 

3. Only in those cases of violent febrile diseases, where little 
or nothing is eaten, and in which the SO3 appears to be con- 
siderably increased, can the conclusion be drawn that this in- 
creased elimination is due to an increased decomposition of 
those constituents of the body. 

§ 131. Phosphoric Acid."^ 

The most convenient and best method for estimating quanti- 

* A. Winter, Beitrage zur Kenntniss der Urinabsonderung bei Gesunden, 
Griessen, 1852. F. Hosier, Beitriige zur Kenntniss der Urinabsonderung, Gies- 
sen, 1853. W. Brattler, Ein Beitrag zur Urologie, Miinclien, 1858. H. Krabbe, 
Ueber die Menge der Pbosphorsilure im Harn, etc., Vircbow's Arcbiv, 1857, 



QUANTITATIVE CHANGES IN THE URINE. 505 

tatively the amount of pliosplioric acid in the urine is the volu- 
metric method with oxide of uranium, described in § 67. 

Formerly ferric chloride was used for this purpose instead of 
the oxide of uranium, but it gives much less accurate results. 
The investigations mentioned above, and those reported in the 
following pages, were mostly performed with ferric chloride. 
Yet the results agree closely enough with those which were ob- 
tained by H. V. Haxthausen under my direction, and in which 
the oxide of uranium was used. 

There are numerous series of investigations concerning the 
daily and hourly elimination of phosphoric acid in health. 
Breed found as the average amount in twenty-four hours in four 
individuals 3 '7 grm. ; Winter, in one person, 3*7, in a second, 
4'2, and in a third, 5*2 grm. ; in the same person at two different 
times, 2*4 and 3 '7 grm. ; Neubauer found in one individual 3*1 
grm., in another only 1*6 grm. ; Aubert found 2*8 grm. ; v. Hax- 
thausen found in a large series of investigations upon his own 
urine from 3*11 to 5*58 grm. ; Kiesell, 2*7 to 2*9 grm. "We may, 
therefore, consider about 3*5 grm. as the average amount of 
phosphoric acid eliminated in twenty-four hours by a male 
adult, although it must be observed that the individual ave- 
rage may vary very considerably from this figure. The average 
hourly amount is, therefore, about 0*15 grm. Winter has cal- 
culated the amount of PO^ for the weight and height of the body, 
and found that the average hourly amount for 100 kilogr. is 0*27 
grm., and for 100 ctm. is 0*1 grm. 

The daily and hourly variations existing in the same indi- 
vidual under conditions of health are very great. Thus, Neu- 
bauer found that the daily maximum in one individual was 2-16 
grm., the minimum, 1*21 grm. ; in another, the maximum was 4*88 
grm., the minimum, 2*44 grm. ; Hosier found as the maximum, 
4^86 grm., as the minimum, 2*40 grm., etc. Still greater dif- 
ferences are found when the hourly amounts eliminated are 
compared with each other. I found in a long series of obser- 
vations in the same individual that the maximum hourly elimi- 

xi., p. 478. H. V. Haxthausen, Acidum phosplioricum urinae et excremento- 
rum, Diss, inaug., Halle, 1860. E. Bischoff, Die Ausscheidung der Phosphor- 
saure im TMerkorper. A. Riesell, Ueber die Phospliorsaureausscheidung im 
Ham bei Einnahme von kohlensaurem Kalk (Hoppe-Seyler, Med.-cbem. Un- 
tersuchungen, Heft 3, 



506 SEMIOLOGY OF EIJMAN URINE. 

nation was 0*216 grm., tlie minimum, 0*085 grm. ; both extremes 
occurred on one day, while the whole series of observations 
lasted during ten days. 

The observations of Winter, Hosier, Haxthausen, and myself, 
which exactly agree, show that the hourly elimination of phos- 
phoric acid is very regular, and in all of the individuals exam- 
ined by us shows a very uniform course. It begins to rise in 
the afternoon hours (after the principal meal), reaches its maxi- 
mum in the evening, falls during the night, and reaches its 
minimum in the forenoon hours. 

The following table shows these differences in the various 
portions of the day in four individuals. The amount of PO^ 
eliminated in one hour : 





Afternoon. 


Night. 


Forenoon. 


By A, 


was 0*18 


0*20 


0*13 grm 


" B, 


''■ 0-28 


0*21 


0*11 '' 


" c, 


'' 0*18 


0-16 


0*10 '' 


" D, 


'' 0*11 


0-14 


0-11 '' 



This table is instructive by showing how every general rule 
is modified in different persons by the individual peculiarity. 
In B, the curve is the steepest, the difference between the after- 
noon and the forenoon being the greatest. In this case, the 
greater part of the PO5 taken with the food was eliminated 
quickly, the summit of the curve falling in the afternoon hours. 
In the case of C, the elimination took place more slowly, the 
summit of the curve falling in the evening hours. In the case 
of D, the elimination occurred still later, perhaps on account of 
slower digestion, and the summit of the curve fell in the night 
hours, although D took his principal meal at the same hour as 
A, B, and C, at one o'clock p.m. 

As to the causes upon which the increase or the diminution 
of the phosphoric acid elimination with the urine depend, the 
facts thus far obtained teach us the following : 

1. The phosphoric acid in the urine increases after taking 
phosphoric acid or soluble phosphates into the organism. 

Aubert * found that the amount of PO5 evacuated with the 
urine, the normal amount in twenty-four hours being 2*8 grm., 

* Henle u. Pfeuffer's Zeitschrift fiir ration. Medicin., 1852, ii. 3. 



QUANTITATIVE CHANGES IN THE URINE. 507 

rose after tlie ingestion of 31 grm. of sodic pliospliate to 4*1 
grm. 

Yon Haxthausen found also that there was a regular increase 
in the elimination of phosphoric acid with the urine after tak- 
ing sodic phosphate. 

2. The phosphoric acid in the urine increases or diminishes 
according as more or less phosphoric acid already formed, or 
substances which are capable of being transformed in the body 
into phosphoric acid are taken into the organism with the food. 
It diminishes during fasting, but without entirely disappearing 
during long-continued starvation, as is the case with the chlo- 
rine. As a rule, a greater amount is eliminated upon a meat 
diet, a less upon a vegetable diet. 

Hosier found that during fasting the PO5 diminished almost 
one-half; and that it increased almost to double its original 
amount upon a diet rich in protein substances. 

Schmidt observed that a cat weighing 1 kilogr. upon an un- 
restricted diet eliminated in twenty-four hours 0*30 grm. PO5, 
but on long fasting only 0*107 grm. 

The fact which was proved with certainty above in the case 
of chlorine, and was shown to be very probable in that of sul- 
phuric acid, that their elimination depends not merely upon 
the amounts taken into the organism from without, but that it 
is also regulated by conditions lying within the system, changes 
of metamorphosis, etc., applies also without doubt to that of 
phosphoric acid. Many facts speak decidedly in favor of this 
view. It has been already shown above, that different indi- 
viduals eliminate the phosphoric acid taken with the food 
with varying rapidity. It follows, from the observations made 
by me, that a remarkable diminution of the phosphoric acid 
elimination (0*084 grm. per hour) may succeed a temporary 
increase of the same (0-216 grm. per hour). The phosphoric 
acid elimination is, as a rule, increased by drinking abundantly 
of water simultaneously with that of the urea and chlorine, and, 
indeed, by an amount much greater than that of the phosphates 
contained in the water ; it is, therefore, caused either by the 
increase of the general metamorphosis, or by the increase of 
the excretory activity of the kidneys, or by both together. It 
follows certainly, from these facts, that the organism under cer- 
tain conditions may contain an increased amount of phosphates 



508 SEMIOLOGY OF HUMAN UEINE. 

on account of the retention of those ingested, or a diminished 
amount on account of their increased elimination. It is also 
certain that the knowledge of these conditions has the greatest 
importance for the physiologist as well as the physician, but 
what we do know at present concerning them is partly frag- 
mentary and partly conjectural, possessing no certainty, but at 
the most probability. Although it now appears important and 
even necessary to explain these conditions by accurate series 
of investigations, yet we meet the same obstacles which were 
brought forward above in reference to the determination of the 
analogous conditions in the case of chlorine and sulphuric acid. 
One of these is that all of the phos]3horic acid is not eliminated 
by the kidneys, but the faeces also usually contain phosphates.* 
Therefore, either the amount of the phosphoric acid contained 
in different parts of the body under different circumstances 
must be quantitatively determined by a very large series of 
investigations, or the amount ingested with the food, etc., to- 
gether with that eliminated with the urine and faeces, must be 
accurately estimated. But this wish must remain for a long 
time ungratified on account of the difficulty of the circum- 
stances, and until then our ideas concerning the increase or 
diminution of the phosphoric acid in disease must be only con- 
jectural, and it is not my intention to enter more fully into this 
subject here. 

Riesell found that the amount of phosphoric acid eliminated 
with the urine was diminished after the ingestion of a large 
amount of chalk, since a large portion of it combined with cal- 
cium passed with the faeces. This diminution, however, was 
only temporary (two days), since the phosphate of calcium 
formed in the intestine was later absorbed and eliminated with 
the urine. 

Direct investigations, of which I j)c>ssess a large number 



" Upon tliis point Von Haxthausen "has performed some experiments under 
my direction. He found that the following amounts of phosphoric acid — ob- 
tained, not by ignition, but by extracting the faeces with dilute nitric acid — 
were evacuated with the excrement in twenty-four hours : Average (of sev- 
enteen observations) = 0'666 grm. ; maximum = l*080grm. ; minimum = 0*270 
grm. Hence, the amount separated with the urine is four or five times greater 
than with the faeces. Riesell (see above) found that the amount of phosphoric 
acid in the faeces was increased by the ingestion of chalk. 



QUANTITATIVE CHANGES IN THE UBINE, 509 

(more tlian 1,000), as to the amount of phosphoric acid elimi- 
nated by patients, have taught me the folloAving : 

In acute diseases of a mild grade the following course of the 
elimination is frequently observed : It diminishes someAvhat 
during the first days, probably on account of the scanty diet, 
then increases again gradually as the patient eats more. It 
sometimes exceeds the normal during convalescence with the 
increased ingestion of food. 

In diseases of this kind of short duration, even when they 
are accompanied by severe fever, the diminution of the phos- 
phoric acid is sometimes very inconsiderable and scarcely ob- 
servable. 

Examples. In a young man with severe angina tonsillaris 
febrilis the PO5 on the day of his entrance into the hospital 
amounted to 2*8 grm. An emetic was given, followed by violent 
vomiting. Scanty diet. On the next day PO5 = 1*7 grm. Patient 
became better, \ diet. On the following day PO5 = 2*6 grm. ; 
on the next 2*5 grm., ^ diet. On the following day 3*2 grm. 
PO5. Discharged well. 

Pneumonia levior. The patient was able to be discharged 
well after eight days. PO5 = 2-4— 2-5— 2-9— 2-4— 2-3 grm. 

Severe pneumonia, at the height of the disease : 1*7 — 0'8 — 2*1 
—1-2— 0-9— 21— 1-9— 1-1 grm. 

Severe pneumonia : 1'6 — 1*4 — 2*2 — 2*3 — 1*6 grm. 

Bronchial catarrh with fever : 1*4 — 1*5 — 1*7 — 1'5 — 2*8 grm. 

Convalescence from a severe pneumonia : 3*8 — 2*7 — 3 '2 — 3*5 — 
3-9— 1-8— 2-5 grm., etc. 

The same : 1 '9—5 -6—2 '8—1 '5—3 -2—2 -8 grm. 

Convalescence from a severe febrile bronchial catarrh : 4*8 
grm. 

Catarrh, organ, digest, eczemat. with violent fever. Eapid 
progress, so that the patient was able to be discharged well in 
eight days : 2-3— 2 '6— 2-7— 2-6— 3-4 grm. 

Females, 

Eheumatic fever: 2-1— 2*3 — 2*2 grm. 

Gastric catarrh : 1*1 — 1'2 grm. 

Catarrhal fever : Height of the disease = 1*6 grm. 

Convalescence from typhoid fever =5*2 grm. 

In many cases in which the disease is severe and the food is 



510 SEMIOLOGY OF HUMAIsT UBINE. 

withdrawn for a long time, or toward death, the phosphoric acid 
is much diminished. 

Cases. Girl with severe catarrh, pulmon. febrilis. At the 
height of the disease = 0*7 — 0*5 grm. During convalescence = 
1-3— 2-5 grm. 

Toward death in a case of acute pulmonary tuberculosis: 
0-4— 0-4— 0-3— 0-3— 0-2— 0-1— 0-08 grm. (day of death). 

Pulmonary gangrene with fatal termination: 3*0 — 2*5 — 2*2 — 
0'7 grm. 

In individual cases, however, the PO5 may, during the height 
of an acute disease, considerably exceed the normal, as the fol- 
lowing case shows : 

Severe pneumonia in a man of middle age, who was treated 
and cured with large doses of digitalis : 4'3 — 5'1 — 4'1 — 8*4 — 7*9 
4-5— 2-9— 5-0 grm. 

In chronic diseases the elimination of phosphoric acid shows 
a very irregular progress ; it usually remains below the normal, 
but sometimes increases considerably. Since I possess a large 
number of series (30-40 observations) of investigations in cases 
of this kind, the complete report of which would be tedious, I 
will in the following cases give only the mean, maximum, and 
minimum values. 

3Mes, 

Cases. Pulmonary emphysema. Mean of eight days = 1*3; 
max. = 2*3, min. = 0*6 grm. 

Chronic bronchorrhcea. Mean of eight days = 2*7 ; max. = 4'7, 
min. =1*3. 

Carcinoma of the liver. Mean of eleven days = 2*2 ; max. = 
2*6, min. = 1*6 grm. 

Subacute articular rheumatism. Mean of eighteen days = 
2'4; max. = 3*1, min. = 1'7 grm. 

Hemiplegia following apoplexy. Mean of thirty-five days = 
2 '7 ; max. = 5 '2, min. =1*0 grm. 

Hydruria. Mean of three days =5*0 ; max. =5*8, min. =4*4 grm. 

Dropsy. Stage of diuresis with great increase of the chlorine 
eliminated. Mean of two days = 1*8 grm. 

Females. 

Diabetes insipidus. Mean of fourteen days = 4*8 ; max. = 7*8, 
min. = 3*2 grm. 



QUANTITATIVE CHANGES IN THE URINE. 511 

Ascites. Mean of fifteen days = 3'0; max. = 4*7, min. = V1 
grm. 

Chronic rheumatism. Mean of seven days = 3*3 ; max. = 4'2, 
min. = 2*7 grm. 

Spinal irritation. 2'1 — 2*8 grm. Mean =2*4 grm. 

Amenorrhoea. 2*1 — 2*3 grm. Mean =2*2 grm. 

Scrofula. 2*6 — 5*2 grm. Mean — 3*5 grm. 

Pulmonary tuberculosis. 1'5 — 3*9 grm. (ten days). 

Chronic facial erysipelas. 1"5 — 3*6 grm. (eleven days), etc. 

Brattler gives the following resume, of his investigations in 
disease : The elimination of phosphoric acid is diminished in 
diseases and functional disturbances of the kidneys with gen- 
erally diminished secretion of urine (Morbus Brightii, heart 
lesions), and in diseases of the digestive organs which diminish 
the absorption of the food ingested. It is increased in acute 
febrile diseases by the increased decomposition of the tissues 
containing phosphorus (the increase, however, is never as con- 
stant as in the case of urea), and further in those diseases in 
which by a functional disturbance of the kidneys the phosphoric 
acid has been held back and accumulated in the blood, after 
removal of the obstruction (Morbus Brightii, and cholera). 

Haxthausen observed a diminution of the phosphoric acid 
elimination in intermittent fever during the interval. 

E. Mendel ^ found that in chronic diseases of the brain the 
amount of phosphoric acid eliminated is, both absolutely and 
relatively to the amount of the other solid constituents in the 
urine, less than in healthy persons who eat the same food ; that 
in maniacs its amount is still less, and increases with recovery ; 
that, on the contrary, it is increased after apoplectic and epi- 
leptic attacks. In some cases, after sleep was produced by 
chloral hydrate or bromide of potassium, he found the phos- 
phoric acid surprisingly increased. 

Earthy Phosphates. 
§ 132. Calcium. Magnesium. t 
In order to estimate quantitatively the amount of earthy (cal- 



^ Die Phospliorsaure im Urin von Geliirnkraiiken, Arcliiv f . Psycliiatrie, 
1873, iii., p. 636, et seq. 
\ Beneke, Der phospliorsaure Kalk, etc., Gottingen, 1850. Derselbe, Zur 



512 SEMIOLOGY OF HUMAN UUINE. 

cium and magnesium) phosphates in the urine, different methods 
may be used according to the purpose of such investigation. 

1. The amount of earthy phosphates is determined collectively 
according to Beneke's method. (§ 91, 1.) This method gives a 
result very quickly, but naturally is only suitable for approxi- 
mate estimations. 

2. The amount of the earthy phosphates is estimated collec- 
tively according to ]3age 255, b, by precipitating them with am- 
monia, washing the precipitate, dissolving in hydrochloric acid, 
and estimating the phosphoric acid in the solution volumetri- 
cally. In this way the true weight of the earthy phosphates is 
not found, but only that of the phosphoric acid combined with 
the earths. 

Or we may estimate : 

3. The calcium and magnesium according to § 76. 

In order to be able to draw further conclusions from the re- 
sults which have been obtained by the one process or the other, 
the following may serve as indications : 

Beneke considers 1'2 grm. as the normal quantity of earthy 
phosphates which are passed with the urine in twenty-four 
hours by a healthy active man. 

Lehmann passed in twenty-four hours 

With ordinary diet, . . 1 -09 grm. of earthy phosphates. 
With purely animal diet, 3-56 '' 

Bocker evacuated on the average 1*48 grm. daily. 

Hosier found that the amount of phosphoric acid combined 
with the alkaline earths (not earthy phosphates, therefore), 
was in his own case, I., during six days in April; II., during 
four days in October : 
I. 

Per Day. Per Hour. 
Mean, . 1-152 0-048 
Maximum, 1-800 0-075 
Minimum, 0-370 0-015 

Physio] ogie und Patliologie des pliospliorsauren und oxalsauren Kalkes, 2. 
Beitrag, Gottingen, 1850. Kletzinsky, Heller's Archiv, 1852, p. 270, et seq. 
C. Neubauer, Ueber die Erdphospliate des Harns, Journ. f. prakt. Cliem., Bd. 
67, p. 65, et seq. F. Huenke, De phosphatum terrarum in urinae quantitate, 
Diss, inaug., Berlin, 1859. A. Riesell (see tlie preceding section). S. Soborow, 
Ueber die Kalkausscheidung im Harn, Centralbl. f. d. med. Wiss., 1872, p. 609. 



n. 




Per Day. 


Per Hour. 


0-390 


0-015 grm. 


0-660 


0-027 '' 


0-170 


0-007 '' 



QUANTITATIVE CHANGES IN THE URINE. 513 

In anotlier healtliy indiyiclual tlie hourly mean was from 
0-015 to 0-019 grm. 

Hegar found that the mean amount of phosphoric acid com- 
bined with the alkaline earths was, in his own case, 1*31 grm., 
the observation lasting eight days ; a half year later the mean 
daily amount of a four days' observation was 0*902 grm. 

Neubauer obtained, as the result of very numerous investiga- 
tions, the following values, which deserve the greatest confidence 
on account of the great number of observations (52) and the ac- 
curacy of the methods employed. 

The average mean amount of earthy j)hosphates which are 
passed with the urine by an adult man in twenty-four hours, is 
from 0-941 to 1-012 grm. The average maximum ==1-138 to 1-263 
(highest number = 1-554). Average minimum = 0-8 (smallest 
amount =0-328 grm.). 

The daily amount of calcic phosphate averaged 0-31—0-37 grm. 
Its average maximum =0-39 to 0-52 gTm. (largest amount=0-616 
grm.). Average minimum = 0-25 (smallest amount =0-15 grm.). 

C. Bodeker ^ found that the daily amount of CaO passed with 
the urine by nine young men varied from 0*2 to 0-6 grm. The 
mean was 0-32 grm. 

The magnesic phosphate averaged 0-64 grm. The average 
maximum =0-77 (largest amount=0-938 grm.). Average mini- 
mum=0-5 grm. (smallest amount=0-178 grm.). 

On the average, therefore, one equivalent of the phosphate of 
calcium is evacuated to three equivalents of the phosphate of 
magnesium, or in 100 parts 33 of calcic phosphate and 67 of 
magnesic. 

According to the investigations of Neubauer, calcium salts 
when ingested do not appear in the urine, or only to very slight 
extent. On the contrary, W. Roberts found that after eating, 
the earthy phosphates were considerably increased in the urine, 
almost doubled. 

The experiments of A. Eiesell show than an increase of 
earthy phosphates in the urine took place after the ingestion 
of a large amount of chalk, and at the same time an increase in 
proportion to the amount of phosphoric acid combined with, 
the alkalies. He found that under normal conditions of the 

* Zeitschr. f ration. Med., 1861, p. 164, et seq. 
33 



514 SEMIOLOGY OF HUMAN URINK 

total amount of pliosplioric acid contained in tlie urine (from 
2*7 to 2*9 grm. in tlie twenty-four hours) about | was combined 
with the alkalies and 4 with the alkaline earths. After the in- 
gestion of chalk, however, the proportion changes during the 
first two days to about equal parts {\ : J), together with a dimi- 
nution in the total amount of phosphoric acid contained in the 
urine (from 1*3 to 1*6 grm. in twenty-four hours), while there is 
an excess in the faeces. In the next two days, when the amount 
of PO5 has again increased in the urine (2*2 grm. in twenty-four 
hours), the proportion becomes reversed, so that about f of the 
phosphoric acid eliminated with the urine is combined with the 
alkaline earths and only \ with the alkalies. During these last 
two days the urine also contains a sediment of the phosphate 
of calcium, which had formed within the urinary passages. 

In disease the absolute amount of the earthy phosphates as 
well as the relative proportion between the calcic and magnesic 
phosphates appears to vary very much from the above-men- 
tioned normal. Thus it is almost universally accepted that in 
certain diseases of the bones (osteomalacia, rachitis, etc.) the 
elimination of the earthy phosphates, especially of calcic phos- 
phate, with the urine is very much increased. For the com- 
plete explanation of this symptom, important not merely to the 
pathologist but also to the therapeutist, still more numerous 
and careful investigations are desirable. But these, in order to 
give information concerning the metamorphosis of the earthy 
phosphates as they naturally would, must take account of the 
earthy phosphates eliminated not merely with the urine but 
also with the faeces. 

An increase of the earthy phosphates, especially of the calcic 
phosphate, has special importance to the physician, when it 
leads to the formation within the urinary passages of a sedi- 
ment which may give rise to the formation of urinary gravel or 
calculi. For further particulars on this point consult § 135, 
under the head of calcic phosphate calculi. 



The urinary constituents considered in the previous sections 
are those whose quantitative estimations are, for the purposes 
of the practising physician, of especial importance, since they 
give the most indications for judging of the processes of meta- 



QUANTITATIVE CHANGES IN THE UEINE. 515 

morpliosis in the body, and, moreover, the methods of their 
quantitative analysis are relatively simple. 

In certain cases, however, it is desirable to estimate the 
amount of some other urinary constituents, normal and abnor- 
mal. "We will consider these in the following section. 

§133. Potassium. Kkeatinin. Leucin and Tyrosin. Aixantoin. 
Lactic Acid. Oxymandel Acid. Carbonic Acid. 

The quantitative estimation of the amount of potassium elimi- 
nated with the urine is performed according to the familiar 
methods. (Compare § 78 and § 79.) In many cases this is 
of interest to the physician, since a diminution as well as an 
increase of this substance in the organism is regarded by many 
as the cause of diseased disturbances. The statements of 
Weidner may assist in judging of the results obtained by such 
investigations. This observer evacuated in twenty-four hours 
on the average 3*91 grm. of KO (max. =: 59, min.= 2 grm.). He 
found that the proportion of potassium and sodium in the urine 
was as 1 : 1'35. 

Kreatinin. For its properties consult § 3, and for the methods 
for estimating it in the urine § 74. 

The average daily amount in the urine of men is about 1 
grm. 

Neubauer " found in his own urine from 0*6 to 1*3 grm., 
mean = 1 grm. of kreatinin. In several other adults he ob- 
tained the same results (0*8 — 0*9 grm. per clay). Loebe t 
obtained a similar average (0*839 grm. per day) from ten ob- 
servations upon two men. K. B. Hofmann % found in twenty- 
seven observations upon himself as the daily average 0'681 
grm. (max. = 0'810, min. = 0-519 grm.). In other persons he 
found somewhat more : mean = 0'99 grm. per day. The urine 
of infants (nursing) contains no kreatinin. Women eliminate 
somewhat less than men. The daily average in women (of 
seven observations) was 0*65 grm. 

The kreatinin of the urine originates from the kreatin of 
the muscles, which, before it has left the body (probably in the 

*Annal. d. Chera. u. Pliarniac, Bd. 119, page 27, et seq. 
\ Journ. f . prakt. Cliemie, 1860, page 170, et seq. 
ivircliow's ArcMv, 1869, Bd. 48, page 358, et seq. 



516 SEMIOLOGY OF HUMAN UBINE. 

kidneys), is changed into kreatinin. The muscular tissue of 
the meat which is eaten partly contributes to this, and partly 
the muscles of the body, when they are decomposed by meta- 
morphosis. An increased muscular activity, when not accom- 
panied by a chemical decomposition of the muscular tissue, 
produces no increased elimination of kreatinin, as Nawrocke,* 
Yoit,t and Meissner % have shown. 

Hofmann found that the amount of kreatinin in the urine 
diminished during starvation. It was considerably increased 
by a meat diet even in children, who otherwise eliminated little 
or no kreatinin with the urine. Bodily activity, on the con- 
trary, had no influence upon the amount of kreatinin. 

We must consider also the increase or diminution in the 
elimination of kreatinin with the urine in pathological cases. 
In this respect the facts hitherto obtained teach us the follow- 
ing : Munk found the kreatinin increased in the urine in acute 
diseases, like pneumonia, the efflorescent stage of typhoid, and 
intermittent feA^er, and diminished during convalescence from 
acute diseases. Hofmann came to the following conclusions: 
Purely local affections were without influence ; febrile diseases 
produced an increase (at the expense of the muscular tissue 
of the body) ; diseases attended with scanty nourishment pro- 
duced a diminution. In advanced degeneration of the kidneys 
the amount of kreatinin in the urine diminished even when 
an abundance of meat was eaten (probably because the kidneys 
were unable to change the kreatin present in the blood into 
kreatinin). H. Senator § found it considerably diminished in 
the urine in two cases of tetanus — a disease in which, however, 
there is an excessive activity of the muscles. This fact, which 
is according to the earlier opinions an apparent paradox, finds 
its explanation in the above-mentioned experience of Voit and 
others. 

Whether there is an increased elimination of kreatinin or 
not in trichinosis, as would be expected, must be decided by 
further investigations. 

Leucin (see | 36) and tyrosin (see § 37, § 48, and page 425) 

" Centralbl. f. d. med. Wissensch., 1866, page 625. ^ 

f Zeitscli. f. Biologie, Bd. 4, page 114, et seq. 

tZeitscli. f. ration. Medic, 1868, Bd. 31, p. 234, et seq. 

§ Ueber die Bescliaffenheit des Harnes im Tetanus. Vircliow's Arcliiv, Bd. 48. 



QUANTITATIVE CHANGES IN THE UBINE. 517 

usually occur together. Tliey are the products of the decom- 
position of nitrogenous substances, and are, therefore, found 
in parts of the body Avhich have been preserved for a long 
time in alcohol, whereby the tyrosin which is insoluble in 
alcohol separates in the form of a white deposit. When the 
metamorphosis is normal, they form in the body in, at the 
most, small amounts ; but when there is an abnormal, putrefac- 
tion-like decomposition (gangrene, etc.), they form in larger 
quantity. In such cases they may also pass over into the 
urine, and their importance for the physician rests upon this, 
that from their abundant presence in the urine we may infer 
the existence of such an abnormal decomposition within the 
organism. They take the place of the diminished, or even ab- 
sent, urea (compare page 478). Up to the present time they 
have been found especially in acute atrophy of the liver and in 
acute phosphorus poisoning, and in a few cases of leucocy- 
thasmia, typhoid, small-pox, etc."^ 

The presence of allantoin in the urine has, up to the present 
time, but slight importance for the physician. It has been 
found by Frerichs and Stadeler in the urine of dogs when the 
resj^iration has been impeded; also by Kohler.f SchottinJ 
found it in the urine of men also after taking tannic acid. 

The presence of lactic acid (§ 30) and oxymandel acid (§ 38) in 
the urine of persons suffering with acute atrophy of the liver, 
need only be mentioned here. 

A. Ewald § has in a number of cases of persons suffering with 
acute diseases determined the amount of carbonic acid in the 
urine, and has found that it is regularly higher during the 
febrile stage than when there is no fever. 

The quantitative estimations of albumen and sugar, which are 
sometimes necessary, have been already treated in § 97 and 
§ 104 



"Compare Frerichs and Stadeler in Miiller's Arcliiv f . Anat. und Pliysiol., 
1854, page 393, et seq. Schmeissner, Arcliiv d. Pliarmac, October, 1849, Bd. 
150, page 11. 0. Scliultzen und L. Eiess, Ueber akute Pliospliorvergiftung u. 
Leberatropbie, Berlin, 1869. 

f De allantoini in urina impedita respiratione praesentia, Diss. Hal ens, 1857. 

ILebmann's Hdbcb. d. pbysiol. Cbemie, 1859, page 93. 

§ Ueber den Kohlensauregebalt des Harns, Arcbiv von Reicbert und DuBois- 
Raymond, 1873. 



518 SEMIOLOGY OF HUMAN UBmE. 

§ 134 Concluding Observations. 

The attempt lias been made above to explain the importance 
of the quantitative changes of the nrine for the physician, in 
such a Avay as to include the semiology and significance of the 
different diseases. But the information, which the physician 
may obtain from the observation of the urine in disease, has 
by no means been exhausted. He is enabled to draw still 
more important conclusions in reference to diagnosis, progno- 
sis, and treatment than the single changes in the urine w^ar- 
rant in themselves by observing various changes which are 
present simultaneously or follow each other closely, or even by 
going a step farther and comparing tliese with abnormities 
in other secretions, as the intestinal, the lung exhalations, the 
perspiration, etc.,. which give him information as to the general 
metamorphosis in the organism. It is not my intention to go 
any farther into this domain, which is still enveloped in dark- 
ness, and has, for the most part, only recently been investigated. 
I wish only to give a few cases from which the physician can 
draw important inferences, and with relatively little trouble. 
The following cases have all been taken from real life, and have 
been observed by me in the manner to be described. In order 
to avoid being tedious, I only give a sketch of them, bringing 
out the principal features, and adding a few general observa- 
tions, where necessary for an explanation: 

1. A girl, 20 years old, who had been ailing for a long time 
and suffering with indefinite symptoms, which were considered 
to be due to beginning pulmonary tuberculosis, had great 
thirst, diminished perspiration, and no fever. She passed a 
very large amount of urine (3,000 to 6,600 cc. daily) of high 
specific gravity (1'025 to 1'034), and it contained a considerable 
amount of sugar. The diagnosis was without any doubt dia- 
betes mellitus. After the use of an animal diet, meat and 
gluten bread, together with the administration of alkalies (mag- 
nesia and bicarbonate of sodium) and opium, improvement took 
place, but it was not of long duration. An intervening j)neu- 
monia fulminans quickly proved fatal. 

In contrast to this case of decided diabetes mellitus, the 
author has during the last year observed a large number of 
cases in which the urine has contained sugar, usually tempo- 



QUANTITATIVE CHANGES IN THE URINE. 519 

rarily and after the ingestion of smaller or larger amounts of 
sugar, without the general health being disturbed thereby to 
any great extent. This occurred usually in men of advanced 
life (although there were a few cases in women) who lived well 
and suffered more or less with symptoms of arthritis (rich man's 
gout, podagra, etc.). In some of these cases the urine contained, 
together with the sugar, considerable quantities of albumen also. 
Some of these patients the author has had under his observa- 
tion and treated (usually with slight attacks) for a long time^ 
(ten years and more), without having seen any dangerous com- 
plications occur, or even with only a slight disturbance of the 
general health. 

Possibly this report may serve to give consolation to those 
patients to whom the fear brings more danger than the disease- 
itself : that glycosuria is not in all cases dangerous. 

2. A woman, 36 years old, with a puffy, pale, ancemic look,, 
and blue rings about the eyes, suffered with all sorts of nervous 
symptoms (mental hyperaesthesia with a tendency to spasms), 
such as are ordinarily included under the name of "hysteria." 
A more accurate examination showed that the amount of urine 
passed was very much increased (between 3,000 and 4,000 cc). 
The urine was pale yellow to bright yellow, its coloring matters 
were rather diminished than increased (3 to 5) ; it was only feebly 
acid, even frequently alkaline, and the free acid was decided- 
ly diminished (0 to 0'5).^ Its specific gravity was below the 
normal (1*012 to 1*015), but the amount of the solid constituents 
was decidedly increased (80 to 120). This increase included 
most of the urinary constituents (urea 40 to 49, chlorine 20 
to 30, phosphoric acid 5 to 9, and sulphuric acid 3 to 5 grm.). 
The urine contained no trace of sugar. Diagnosis : diabetes 
insipidus. The patient obviously suffered from an abnormal 
increase of the metamorphosis of tissue (only that of the blood 
globule being decidedly diminished, and the temperature was 
also below the normal), the emunctories of the body were 
almost all increased, and since the patient lived in poor circum- 
stances, this increased elimination could not be made up by an 
abundant ingestion of food, so that her nutrition rapidly fell : 
she lost in weight about three pounds in two days. "With an 
abundant amount of concentrated food combined with tonics 
(preparations of quinine and iron) and opium, the secretion of 



520 SEMIOLOGY OF HUMAN URINE. 

■urine gradually became normal, tlie appearance of the patient 
improved, lier strength increased, and the nervous symptoms 
disappeared. Since, however, the patient returned to her for- 
mer way of living, the attacks were repeated — diabetes insipidus 
intermittens. 

1 have frequently observed exactly analogous cases in conse- 
quence of drinking an excessive amount of water after the care- 
less employment of water cures, undertaken in consequence of 
false indications or continued for too long a time. 

3. A strong man, in consequence of exposure to cold, was 
seized with severe tearing pains in the region of the neck and 
shoulder (rheumatismus nuchae). The skin became cool and 
dry, and the amount of perspiration diminished ; his urine, how- 
ever, was increased (3,000 to 4,000 cc). The amount of coloring 
matter in it was about normal (4 to 5), and also that of the free 
acid (1*8 to 2*3). Its specific gravity, however, Avas far below 
the normal (1*006 to 1*008), and the amount of the total solid con- 
stituents was rather diminished (36 to 40 grm.), also that of the 
individual substances, the urea, chlorine, phosphoric acid, and 
sulphuric acid was rather below than above the normal. Diag- 
nosis : hydruria. The increase of the urine was evidently only 
dependent upon an increased elimination of water by the kid- 
neys, which made up for the diminished separation of water 
by the skin and lungs. Although the hydruria continued for 
several days, yet the strength and weight of the patient did 
not diminish. After treatment with diaphoretics, which pro- 
duced an increase of the perspiration, the polyuria gradually 
disappeared, and also, after the use of wet cups, the rheuma- 
tismus nuchae. 

4. In the case of a young man with organic heart disease (in- 
sufiiciency of the bicuspid valve with consequent hypertrophy 
and dilatation of the right ventricle), the amount of urine gradu- 
ally diminished (from 1,600 to 1,200, 800, and 600 cc.) ; at the 
same time the elimination of the urea (26, 20, 18 grm.) and 
chlorine (8, 5, 3, grm.) diminished considerably, and to a less 
extent that of the phosphoric acid (2 to 1*5 grm.) and sulphuric 
acid (1*5 to 1 grm.). Dropsical effusion into the abdominal 
cavity and oedematous swelling of the extremities, especially 
the lower, followed. After the administration of powerful diure- 
tics (infusion of digitalis and acetate of potassium) the amount 



QUANTITATIVE CHANGES IN TEE VBINE. 521 

of urine increased considerably (3,000, 4,000, 4,500 cc), and with 
this very considerable amounts of urea (50, ^b, 60 grm.) and 
chlorine (25, 30, 33 grm.) Avere eliminated, while the sulphuric 
and phosphoric acids scarcely exceeded the normal amount. 
In this case evidently large quantities of water, urea, and chlo- 
rine, instead of being evacuated with the urine, had gone over 
into the dropsical effusions and had accumulated in them, and 
after the abundant diuresis were separated with the urine. 

The same course, diminution of the secretion of urine, and 
simultaneous dropsical swellings with an increased elimination 
of water, urea, and chlorine with the urine after the use of 
diuretics, was repeated several times afterward in the same 
case. 

5. An elderly man, who suffered with a very marked rigidity 
of the arteries, was attacked with a pretty severe bronchitis, 
extending over both lungs. The condition of the patient was 
subject to extraordinary variations ; violent attacks of dyspnoea 
with a small rapid pulse of 100 to 126 beats, which sometimes 
caused fainting, alternated with a tolerable condition. The ex- 
amination of the urine showed that there were similar variations 
in the metamorphosis of tissue, which ran a parallel course with 
the general condition of the joatient. On some days only 300 
or 400 cc. of urine were passed, and on others 1,200 to 1,500 cc. 
Its color varied from bright yellow to red ; the coloring matter, 
from 2 to 18, was, howei^er, as a rule, increased (influence of the 
fever) ; the specific gravity w^as about the average (1*012 to 
1*023), the amount of solid constituents was, on the average, far 
below the normal (18 to 30 grm.), the amount of urea was also 
very varying, but was also, in spite of the fever, far below the 
normal (12 to 25 grm.) ; the urine frequently contained a sedi- 
ment of urates. The chlorine showed the greatest variation ; 
it was always considerably diminished, and sometimes only 
traces were found in the urine (0*1 to 5 grm.). The phosphoric 
and sulphuric acids were also diminished. These considerable 
variations in the metamorphosis of the patient, depending upon 
a shattered constitution, taken in connection wdth the existing 
lung disease, led to the fear of a speedy collapse. In fact 
this took place very suddenly. On one evening after the patient 
felt better and more brisk than usual, he complained of great 
weakness in the night, and a rapidly spreading oedema of the 



522 SEMIOLOGY OF HUMAN URINE. 

lungs, which withstood all counter-irritants used, proved fatal 
in a few hours. 

6. A man, 57 years old, in consequence of a severe exposure 
to cold upon a journey, was attacked with a pneumonia of the 
left side, which was, from the beginning, treated with cupping 
and digitalis in large doses (J- drachm daily). The patient had 
very severe fever ; the urine was less scanty than in other simi- 
lar cases (at the height of the disease, 900, 1,000, 1,950, 1,500, 
1,350, and 1,200 cc), very high colored, the amount of coloring 
matter considerably increased (28 to 32), the specific gravity 
about normal (1*018 to 1-024), and the solid constituents usually 
below but sometimes above the normal. The urea was increased 
(40 to 60 grm.), the sulphuric acid at first increased (3*5 to 4 
grm.), but later was below the normal (1*8 — 1*1 — 1*6 grm.), and 
the phosphoric acid was almost always increased (4 — 5 — 7 — 8 
grm.). The chlorine, during the first two days, was present 
only in traces, increased gradually (3 — 4 — 7 grm.), and reached 
the normal from the eighth day. The patient improved very 
rapidly in spite of his advanced age, and in spite of the fact that 
he had previously had pneumomia, so that his lungs were pro- 
bably not entirely normal, and was able to leave the hospital 
well in ten days. This case is especially interesting in refer- 
ence to the metamorphosis, since it shows the favorable action 
of the digitalis. There was in this case, as in all violent fevers, 
an increased decomposition of the constituents of the body, and 
unusually large quantities of urea and urinary coloring matter 
were formed, and increased amounts of phosphoric and sul- 
phuric acids Avere set free from their organic compounds. But 
the secretion of urine was, in this case, owing no doubt to the 
influence of the digitalis, much more abundant than in other 
similar cases, whereby the decomposition products formed were 
quickly separated from the body, and convalescence hastened. 
I do not mean to say that the action of digitalis in such cases 
is limited to this effect, but only mention that method of action 
as an apparent One in this case. 

7. A man suffered with a chronic affection of the liver and 
stomach with organic change which could be ascertained, al- 
though its exact nature could not be diagnosticated. Long-con- 
tinued disturbances of digestion and severe pain had exhausted 
his strength, and, therefore, it was desirable to obtain a nearer 



QUANTITATIVE CHANGES IN THE URINE. 523 

insight into tlie metamorpliosis of tlie patient, partly to est^iblisli 
the indication for the means to be first used for the symptoms, 
and partly for the purpose of giving a prognosis. For this 
reason the patient's urine was examined for several days in suc- 
cession, and the following were obtained as the average propor- 
tions : The quantity was about normal (1,500 cc), the color 
bright yellow, the coloring matter somewhat below the normal 
(3), the reaction feebly acid, and the free acid considerably di- 
minished (0-4). The specific gravity was somewhat low (1'014), 
and also the solid constituents (42 grm.) ; of the single consti- 
tuents, the urea (29 grm.) and sulphuric acid (14 grm.) were 
somewhat diminished, while the phosphoric acid (3'3 grm.) was 
about normal, and the chlorine (10 grm.) was rather in excess 
of the normal. This showed at that time a good condition of 
the digestion (chlorine and PO. abundant), but, on the contrary, 
a somewhat diminished decomposition of the nitrogenous tis- 
sues (urea and SO3 below the normal), and also a diminished 
metamorphosis of the blood globule (small amount of pigment 
and considerable diminution of the free acid). The last part of 
the diagnosis was confirmed by the pale anaemic appearance of 
the patient. In consequence of this information the patient 
received a good diet, with tonic drugs, whereby his strength 
and vital energies were, for a time at least, increased, although 
the complete cure of the organic changes forming the principal 
trouble could not be expected. 

8. There are cases in which a febrile increase of the meta- 
morphosis can be recognized almost solely by the composition 
of the urine. The pulse is entirely quiet, the temperature of 
the external parts of the body scarcely increased, the appetite 
but little diminished, and yet there exists an increased tendency 
to the decomposition of the constituents of the body and a ces- 
sation of the excretory activity of the kidneys, a condition which 
may be especially dangerous when, with an existing disease of 
an important internal organ, like the lungs, liver, etc., it gives 
rise to congestion of this organ, which, if long continued, easily 
leads to organic changes or increases any such already present. 
The following is a case of this kind. 

A very powerful man, 48 years old, with a broad, full chest, 
came with symptoms which pointed to a commencing pulmo- 
nary tuberculosis. He had for a long time had a cough with 



524 SEMIOLOGY OF HUMAN URINE. 

expectoration, sliglit dulness of percussion over tlie apex of the 
right lung, with ill-defined, almost bronchial, respiration and 
rales at this point. His respiratory power was less than corre- 
sponded to the size of his body ; fulness of body and strength 
had diminished somewhat during the last month. His pulse 
was, however, entirely quiet (60 to 63), his appetite was tolera- 
bly good (i diet with various extra dishes), the temperature 
of the extremities was not increased, and only in the night 
there was sometimes profuse perspiration. The urine, on the 
contrary, was remarkably abnormal ; it was very much dimin- 
ished (400 to 600 cc), almost always turbid, with a sediment of 
uric acid ; very high colored, and the coloring matter increased 
(16 to 24) ; the specific gravity was very high (1-022 to 1*028), 
the urea was rather above the average (28 to 35 grm.), the chlo- 
rine very much diminished (3 to 5 grm.), and the phosphoric 
acid (2*5 grm.) and sulphuric acid (1*6 grm.) were somewhat 
below the normal. The excretory activity of the kidneys was, 
therefore, decidedly diminished, and since at the same time 
the decomposition of the constituents of the body was in- 
creased, the blood was overcharged with irritating ingredi- 
ents. It happened that the patient had for a long time pre- 
viously suffered with a chronic skin disease (probably psori- 
asis), which had disappeared six months before. There existed 
here, therefore, several conditions together, w^hich must have 
caused an excessive activity of the lungs, and thereby an in- 
crease of the disorganization to be expected in them. (An ac- 
curate examination revealed, in spite of the slow and quiet 
arterial pulse, an increased activity of the right ventricle of the 
heart and an evident strengthening of the pulmonic second 
sound, an overloading of the lungs with blood : at the same 
time the patient complained of considerable dyspnoea and 
tightness of the chest.) The principal indication appeared to 
be to free the lungs of the patient from the irritation caused by 
the accumulation of excrementitious substances in the blood 
by increasing the secretion of urine. He was given mild diu- 
retics and blood-purifying drugs (infusion of digitalis with ace- 
tate of potassium ; a tea of the viola tricolor). In general, as 
the secretion of urine increased, the patient felt freer in the 
chest, and much more comfortable in his general condition, so 
that, after a while, he was able to be discharged much improved. 



QUANTITATIVE CHANGES IN THE URINE, 525 

Since, however, lie could not and would not pursue a desirable 
mode of living outside of the hospital, and, moreover, was an 
excessive spirit drinker, the disease made new progress, and 
he returned to the clinic after six months with settled pulmo- 
nary tuberculosis, and died there a few days later. 

9. A man, 45 years old, was attacked suddenly with all of 
the symptoms of a violent febrile disease : chills and heat, loss 
of appetite and bloody urine. Within one and a half days an 
oedematous swelling spread over the whole body with the ex- 
ception of the face. When the patient was admitted a few days 
later into the clinic at Giessen, the symptoms were the same 
as those given except with the addition of violent vomiting. 
During the first three days of his stay there the urine had the 
following apjDearances : Its amount was somewhat below the 
normal (900 to 1,500 cc), and its color intense blood-red. Under 
the microscope it was seen to contain unchanged blood cor- 
puscles in considerable quantity, numerous pus corpuscles, and 
a few granular casts. It contained an abundance of albumen. 
The reaction was alkaline, the specific gravity was low (1*010 to 
1*012), the amount of urea was far below the normal (8 to 20 
grm.), the chlorine was considerably diminished (1 to 3 grm.), 
the phosphoric acid somewhat (1*3 to 2*8 grm.) and the sul- 
phuric acid considerably (0*5 to 1*6 grm.) diminished. On long 
standing, a slimy sediment formed in the urine, due to the ac- 
tion of the ammonia upon the pus corpuscles suspended in it. 
The perspiration (sum of the evaporation from the skin and the 
lung exhalation) was far below the normal (460 to 780 grm. in 
twenty-four hours), the ingesta considerably exceeded the ex- 
creta, so that the patient increased in weight ten pounds in 
three days, which naturally was due only to the constantly in- 
creasing dropsical swelling. Diagnosis : Morbus Brightii acu- 
tus. On account of the great danger that uraemia might de- 
velop suddenly under such circumstances, the most powerful 
means were employed to increase the secretion of the kidneys 
and bowels, but without effect. All remedies taken internally 
(sulphate of sodium with acetate of potassium, gamboge with 
carbonate of sodium, croton oil) were vomited again by the pa- 
tient ; applications of decoction of digitalis made over the whole 
body remained without effect ; enemeta of croton oil dissolved 
in linseed oil irritated the rectum to such an extent that it was 



526 SEMIOLOGY OF HUMAN URINE. 

necessary to omit tliem. Tlie excretory activity of the kid- 
neys diminislied daily ; the amount of urine fell from 800 to 
700, 500, and 450 cc. daily, having a specific gravity of from 
1*015 to I'OIO. The amount of urea diminished continuously 
(6 to 8 grm. daily), also the chlorine (0'8 to 1 grm.), sulphuric 
acid (0*4 to 0*6 grm.), and phosphoric acid (1*3 to 1*7 grm.). 
Symptoms of uraemia (vertigo, delirium) developed, which con- 
tinued to increase (coma vigil, sopor) till the patient died, 
scarcely three weeks from the commencement of his disease. 
The section showed the existence of two stages of Bright's 
disease in the kidneys. 

10. A man, 52 years old, of strong physical constitution, 
was attacked with acute Bright's disease, exactly as in the 
above case. Considerable oedematous swelling of the whole 
body, followed quickly by violent febrile symptoms : the blood- 
red urine was rich in albumen and showed under the micro- 
scope the presence of traces of renal casts together with 
numerous blood and pus corpuscles. But in this case power- 
ful diuretics (pills of gamboge and carbonate of sodium, and 
especially applications of the decoction of digitalis which 
were made on a large scale over the whole lower half of the 
body) succeeded in producing an abundant secretion of urine. 
The urine (from the 25th of October to the 1st of November) 
had the following properties : The amount was very much in- 
creased (4,800 to 6,800 cc), the color was red (bloody), the 
reaction neutral or alkaline, the specific gravity low (1*003 to 
1*005), the urea increased (between 45 and 97 grm. daily), also 
the chlorine (20 to 30 grm.), phosphoric acid (11 to 18 grm.), 
and sulphuric acid (4*1 to 4*7 grm.). "With this increase in the 
secretion of urine the dropsical swelling disappeared entirely, 
the symptoms of uraemia (wandering, soitinolence) which ap- 
peared at first ceased, and the patient felt very well. After 
a while a fresh exacerbation came on : violent fever with swell- 
ing of the lips and a phlyctsenoid eruption about the mouth, 
more scanty and very bloody urine. Since the last symptom 
showed a violent inflammation of the kidneys and there was no 
dropsy, diuretics appeared to be no longer indicated, and I 
considered the principal indication to be now to act upon the 
kidneys with remedies to lessen the inflammation. An emulsion 
of cannabis-indica seeds with bitter-almond water was given, 



QUANTITATIVE CHANGES IN THE URINE. 527 

and after two days tlie deep bloody urine became almost color- 
less. 

11. Hcematuria, caused by dissolved hcemoghhin. (Compare 
§ 100.) A young man, 20 years old, always well up to tlie 
present time, complained that lie liad not felt well for about 
eight days. His face was extremely pale, livid in spots, espe- 
cially under the eyes, where there were bluish-red rings ; the 
temperature of the skin was not increased, the pulse w^as rapid 
(90 to 100), small, and feeble. There were mild, tearing, draw- 
ing pains over the greater portion of the body, especially the 
extremities, together with a sensation of weariness and depres- 
sion. There was also a mild catarrh of the organs of respira- 
tion and digestion (loss of appetite, coated tongue, moderate 
diarrhoea), and slight increase in the size of the sjDleen. He 
was received into the clinic, and it was suspected that a ty- 
phoid fever was coming on. This suspicion, however, was not 
realized. The mild febrile symptoms diminished rather than 
increased, the very feeble, often dicrotic, pulse became slower 
and fuller, the temperature did not rise above the normal, but 
usually remained below 37° C, the intellect remained clear, 
while the patient became so weak that he could scarcely raise 
himself, and the anaemic livid appearance was so extreme that 
it reminded one of the algid stage of cholera. The urine was 
of normal amount, and dark brownish-red color (between 7 
and 8 in the color table), similar to, although not quite as dark 
as, specimens which I have seen after the inhalation of arseni- 
uretted hydrogen. (See page 392.) It contained at least 300 
parts of pigment. No blood corpuscles, and in general, no 
morphological elements could be detected under the micro- 
scope. Upon boiling, a very abundant reddish-brown coagulum 
of haemoglobin was formed, the filtrate from which had a feeble 
yellow color. Otherwise it contained the ordinary constituents 
in normal amount, only the chlorides being somewhat dimin- 
ished on account of the scanty diet. • This condition of the 
urine, which had certainly existed before the admission of the 
patient (he could give no explanation of it), lasted about eight 
days and then disappeared gradually. It indicated that the 
disease consisted essentially of a continued extensive decom- 
position of the blood globules within the blood vessels, the 
products of which were eliminated with the urine (perhaps 



528 SEMIOLOGY OF HUMAN URmE. 

partly, also, witli the bile), and wliicli by its intensity and long 
duration produced an oligocytlisemia of bigli grade. The con- 
dition of the urine together with the great depression and the 
pains in the limbs pointed also to scorbutus, but the change in 
the gums as well as the ecchymoses into the skin and subcu- 
taneous cellular tissue, etc., were absent, and also any etiologi- 
cal fact which could play any part in the production of scor- 
butus. 

The patient took mineral acids, at first alone, but later with 
quinine, and during convalescence j)reparations of iron. He 
recovered slowly but completely. 

No cause could be discovered. 

A few months later, without any cause which could be de- 
tected, another attack of heematuria appeared, only shorter and 
less intense than the former one. During this attack, as during 
the first one, the patient w^as entirely free from pain in any 
part of the uropoetic system. 

12. The following case, essentially different from the pre- 
ceding one, and also occurring without any discoverable cause, 
affords an examj^le of vesical Jicematuria. Friedrich P., but- 
cher, 22 years old, never sick before, born of healthy parents 
(the father is said to have suffered from haemorrhoids only), 
was attacked with a mild gastritis with dizziness and ring- 
ing in the ears, and was on that account admitted into the 
clinic. Formerly he had never had attacks of hemorrhage, 
but a few years before his sickness he had frequently had 
nose - bleed. A more accurate examination of the patient 
showed that his urine was blood red, and a further investiga- 
tion showed that he suffered with dysuria, a frequent involun- 
tary impulse and desire to urinate, so that he was forced to mic- 
turate almost every quarter of an hour. The urine, especially 
that last evacuated, was always very bloody. Examination of 
the orifice of the urethra showed nothing abnormal, the poste- 
rior part of the urethra was not tender on pressure, nor did the 
digital examination, -per anum, of the prostate and bladder 
shoAV any abnormity. The plainly bloody-colored urine depos- 
ited after long standing a scanty dark-red sediment, which be- 
came diffused upon shaking and which consisted only of blood 
corpuscles without admixture with pus. If the urine was fil- 
tered, the filtrate appeared to be completely free from blood, 



QUANTITATIVE CHANGES IN THE URINE. 529 

of a clear yellow color, while a dark-red precipitate of blood 
corpuscles remained behind on the filter ; the urine contained, 
therefore, only undecomposed blood globules and no dissolved 
blood pigment. The blood corpuscles came without doubt 
from the bladder, and the cause of their passage into the urine 
was probably a congestive hypersemia of the mucous mem- 
brane of the bladder, which had increased to such an extent as 
to rupture the vessels. 

The treatment was limited to the administration of hemp- 
seed tea with bitter-almond water, under which the patient im- 
proved so much that the dysuria disappeared in a few days, 
and the blood gradually ceased to appear. 

13. The following case is interesting since it resembled most 
delusively a case of hcematuria, the non-existence of which was 
only recognized by the microscope. 

An old man, 72 years old, had had for about five years an affec- 
tion of the bladder, which was chiefly characterized by the fact 
that the patient, who had previously been well and was for his 
age very robust, from time to time after straining, too long re- 
tention, etc., passed a little blood with his urine, and had slight 
pain in the region of the bladder. The simultaneous occasional 
evacuation of gravel had given rise to the suspicion that a vesi- 
cal calculus might exist. He had, therefore, consulted various 
physicians and had been examined several times, but no calcu- 
lus had been detected. Most of the physicians explained his 
affection by the existence of bladder haemorrhoids, and the pa- 
tient had in consequence used Kissingen and Carlsbad w^aters 
without any marked benefit. He had never lost blood with his 
stools. Examination showed no trace of haemorrhoids and no 
enlargement of the prostate. His general health was good and 
his arteries were not rigid. 

The urine of the patient was very strongly acid and deposited 
a sediment of large crystalline masses of uric acid. There was, 
besides, a very abundant dirty-red (cinnamon colored) sediment, 
in wdiich there were large flocculi and which settled pretty 
quickly. Disseminated through the urine it gave it the appear- 
ance of being mixed with blood, and it had been so considered 
by the patient and his various physicians up to this time. 
Under the microscope numerous cellular forms were seen, which 
at first sight appeared to be blood globules, but which upon 
34 



530 SEMIOLOGY OF HUMAN UBIJSfE. 

more careful examination were seen to differ from them in im- 
portant particulars. They were round and reddish colored like 
blood globules, but were somewhat larger {-^l-^J to -^iu'" in dia- 
meter), contained a distinct nucleus, and were not changed by 
acetic acid. (See Plate III., fig. 6, D, a, a.) Together with these 
there were other larger and smaller, irregular, partly caudate 
cells, mostly with an overlying nucleus (Fig. 6, D, bbb), partly 
single, partly (in the flocculi visible to the unaided eye) united 
in shreds, but without any trace of a fibrinous basement mem- 
brane. The sediment also contained normal pus corpuscles, 
which on being treated with acetic acid showed the ordinary 
nuclei. 

From this result the preliminary diagnosis was made of fun- 
gous excrescence (epithelioma) of the bladder, with a tendency 
to acid urine and the separation of uric acid, and he was ordered 
the regular use of Fachinger water and hemp-seed tea, wdth 
acetate of potassium and cherry-laurel water. Under this treat- 
ment the condition of the patient improved greatly. ^ For several 
months in succession the urine was no longer bloody colored, 
and contained instead of the cells of the epithelioma only a few 
pus corpuscles and a few mucous shreds. The troubles of the 
patient were reduced to occasional pains in the glans penis, 
and only the evacuation of the last portion of the urine required 
any straining. 

May the above examples contribute to convince our profes- 
sional brethren that a consideration of the condition of the 
metamorphosis in patients is of value to the practising physi- 
cian, and that an examination into this condition does not in- 
volve such insurmountable difficulties as many appear to think. 
But, finally, I cannot forbear to express the wish, that those phy- 
sicians who undertake to follow the methods suggested above, 
may keep within bounds, and not by keen hypotheses and un- 
founded suspicions overreach the limits of our present know- 
ledge. Such a procedure would serve not only to injure the 
patient who intrusts himself to his care, but also would tend to 
lower in the eyes of the intelligent profession, as well as of the 
public, the value of this certainly legitimate tendency of scien- 
tific medicine, which sets for itself the task of considering the 
chemistry of the metamorphosis in disease in addition to the 
observation of other conditions. 



UBINABY CALCULI AND OTHER CONGBETIONS. 531 



APPENDIX. 

§ 135. Introduction to the Examination of Urinaey Calculi 

AND OTHER UrINARY CONCRETIONS. 

Urinary concretions are deposits whicli form from tlie urine 
within the urinary passages (kidneys, ureters, bladder, or ure- 
thra). They are sometimes small, like grains of sand, so that 
they can be passed with the urine without great difficulty, in 
which case they are usually numerous and, as a rule, crystalline 
(urinary sand, gravel). Sometimes they are larger, from the 
size of a bean to that of an apple, so large that they cannot, 
or only under exceptional circumstances, be passed with the 
urine, but are retained in the calices or pelvis of the kidney or 
in the bladder, and there produce, by their mechanical action, 
irritation, pain, hemorrhage, inflammation, etc., and they may 
also remain sticking in the ureter and urethra, and occlude, 
irritate, and wound these canals (true calculi). 

Most of these concretions consist of the urinary sediments 
which have separated within the urinary passages, and, in- 
stead of being immediately evacuated, unite together into large 
masses or adhere to and incrust a foreign body which has in 
some way gotten into the urinary passages. In this way con- 
cretions already existing may increase in size, new layers of 
sediment being constantly deposited upon them, and they grow 
more or less rapidly. 

Since transitional forms very frequently occur between uri- 
nary gravel and the ordinary sediments from which the gravel 
is formed, and no sharply defined limit can be drawn between 
gravel and the smaller calculi, the distinction between these 
different forms in many cases is a tolerably arbitrary one and 
of no great practical importance. 

On account of the unpleasant and oftentimes even dangerous 
consequences of an existing urinary concretion, its detection is 
naturally of great importance to the physician. To describe 
the manner in which this must be done belongs to special 
pathology and diagnosis. But the recognition of the chemical 
composition of a concretion has also not merely a scientific but 
also a practical interest for the physician, since this only can 
give us the means of preventing, by appropriate medical treat- 



532 SEMIOLOGY OF HUMAN TJRmE. 

ment, the further formation of gravel which irritates mechani- 
cally the urinary passages, or the still more dangerous forma- 
tion of a calculus, or finally the further groAvth of a calculus 
already formed, if we leave out of consideration entirely those 
hitherto rather unsuccessful experiments of dissolving the con- 
cretions by chemical reagents within the urinary passages — ex- 
periments which, as their first essential condition, presuppose 
an accurate knowledge of the chemical composition of the cal- 
culus which is to be dissolved. Even the chemical composition 
of such calculi as are to be removed by an ojDeration (lithoto- 
my or lithotrity) has in addition to a scientific interest not 
rarely a practical one also, since it gives us the means of pre- 
venting by an aj)23ropriate internal treatment the formation of 
new concretions of the same composition in the patient ope- 
rated on. 

The chemical constituents of calculi are essentially the same 
as those which have already been considered under the head of 
urinary sediments, namely : 

Uric acid and urates, 

Xanthin (uric oxide), 

Cystin, 

Calcic oxalate. 

Calcic carbonate. 

Calcic phosphate, 

Ammonio-magnesian phosphate, 

Protein compounds (fibrine, mucus), 

Urostealith, 

as the principal constituents, with which are sometimes mixed 
small quantities of other substances (silica, clay, etc.). 

Many urinary concretions consist chiefly of only one of these 
constituents, while others are mixtures of several of them which 
are either mixed together or form separate layers. 

Since the properties and methods of detection of most of 
these substances have been already described, it will be suffi- 
cient here to point out the general process which must be fol- 
lowed in the analysis of such concretions, and refer to former 
sections for special tests. 

If urinary gravel is to be examined, it is best to subject it to 
a preliminary microscopic examination, since its chemical com- 



URINARY CALCULI AND OTHER CONCRETIONS. 533 

position can frequently be recognized from the form of its crys- 
tals, etc. For the chemical examination, it should be so pre- 
pared as to isolate the granules as completely as possible from 
adhering impurities, such as blood and pus, and they should 
be washed with distilled water. If the granules are large they 
should be powdered. 

If a calculus is to be examined, it should be remembered that 
it not rarely consists of several layers of different chemical 
composition. It should, therefore, be sawed, or better, broken 
in pieces, and a portion of each layer, which appears by its 
looks to be different from the others, should be powdered and 
subjected to chemical examination. It is best in this case also 
to wash the powder with distilled water before the examina- 
tion, in order to separate the infiltrated constituents which do 
not belong to the composition of the calculus. 

I. If as accurate an analysis as possible is desired, and this 
method is to be recommended to those unskilled, it is best to 
begin by igniting a portion of the powder upon platinum foil 
over the spirit lamp. If the substance burns up completely, or 
only leaves, at the most, an unimportant residue, the calculus 
may consist of 

Uric acid or urate of ammonium, 

Xanthin, 

Cystin, 

Protein substances, 

Urostealith. 

In order to further determine of which of the above sub- 
stances the concretion consists we proceed as follows : 

We first test for uric acid. If an evident murexid reaction is 
obtained by treating the powder with nitric acid and ammonia, 
according to page 40, 8, and page 41, a, the concretion consisted 
of uric acid or urate of ammonium. These two may be distin- 
guished by the fact that uric acid is very slightly soluble in 
boiling water, while urate of ammonium dissolves much more 
easily and in larger amount. On cooling it separates from 
this solution and evolves ammonia when treated with potassic 
hydrate. (See page 164, 3). 

Calculi of uric acid are relatively very common, and may 
reach a very considerable size. They are usually colored (yel- 



534 SEMIOLOGY OF HUMAN URINE. 

lowish, reddish, red brown), rarely white, usually liave a smooth 
surface, and are tolerably hard. 

Calculi of urate of ammonium are rare, usually small, of 
lighter (whitish or clay yellow) color, and more earthy in char- 
acter. 

If no murexid reaction is obtained, the combustible calculus 
may consist of 

Xanthin (uric oxide). This substance dissolves in nitric acid 
without effervescence, and after the evaporation of this solution 
a bright citron-yellow residue is left, which is not colored red 
by ammonia, but is dissolved by potassic hydrate with a deep 
reddish-yellow color. (See § 5.) But since guanin, a substance 
recently discovered, but which has not yet been detected as a 
constituent of urinary concretions, gives a similar reaction, care 
should be taken before pronouncing that a urinary concretion 
consists of xanthin. 

Calculi of xanthin are exceedingly rare, and at the present 
time only a few examples are known. They have a light brown 
(whitish to cinnamon brown) color, are tolerably hard, assume 
a waxy lustre on being rubbed, and consist of concentric amor- 
phous layers which are easily separated. 

Calculi of cystin are also quite rare : of dull yellow color, 
smooth surface, crystalline uj)on fracture, and with a waxy or 
fatty lustre. They are quite soft, easily scratched, and the 
powder has a soapy feel. 

Chemically, cystin may be recognized from the following 
properties : It dissolves in ammonic hydrate, and separates 
from this solution on slow evaporation in very characteristic 
crystals, which are regular hexagonal plates. It is also solu- 
ble in the mineral acids and separates from the hydrochloric 
acid solution on slow evaporation in the form of groups of 
diverging needles arranged in the shape of a wheel. It con- 
tains a considerable amount of sulphur. If, therefore, a con- 
cretion containing cystin is dissolved in potassic hydrate, and 
then boiled after the addition of a small amount of a solution 
of acetate of lead, a black precipitate of the sulphide of lead is 
formed, which gives to the mixture the appearance of ink. (See 
§47.) 

Calculi of protein substances (consisting of fibrine or blood co- 
agula) are also very rare. They show no trace of crystallization, 



URINABT CALCULI AND OTHER CONCRETIONS. 535 

evolve upon being ignited an odor of burnt liorn, are insoluble 
in water, etlier, and alcohol, soluble in potassic liydrate from 
which solution a precipitate is produced by acids, swell up in 
acetic acid, and are soluble in boiling nitric acid. 

Calculi of UTostealitli are also very rare.^ When fresh they 
are soft and elastic, similar to caoutchouc. Upon being dried 
they become smaller, brittle, light brown to black in color, and 
are tolerably hard, but upon warming become softer again. On 
being heated they melt without volatilizing, swell up, and a 
very strong odor is evolved, which reminds one of a mixture 
of shellac and benzoin. Boiled in v/ater they become soft with- 
out dissolving. They are easily soluble in ether ; the amor- 
phous urostealith left after evaporation of the ether becomes 
violet on being heated. They dissolve easily in potassic hydrate 
when heated, and are saponified. They dissolve in nitric acid 
with slight evolution of gas and without change of color : the 
residue is colored dark yellow by alkalies. 

II. If the concretion is incombustible or leaves after ignition 
a considerable residue, it may consist of 

Urates of the fixed alkalies (sodium, potassium, calcium), 

Calcic oxalate. 

Calcic carbonate, 

Calcic phosphate, 

Ammonio-magnesian phosphate. 

Calculi consisting solely of the urates of sodium, calcium, and 
magnesium are not of frequent occurrence, but these substances 
are sometimes contained in urinary calculi in larger or smaller 
amount, while the larger part of the calculus is made up of 
some other constituent, such as uric acid or urate of ammo- 
nium. 

In order to determine whether such a calculus contains uric 
acid combined with these bases, the powder is boiled with 
distilled water and filtered while hot. The urates, which are 
more easily soluble in warm water than uric acid, pass through 
into the filtrate. This is evaporated and then ignited. The 
residue which remains contains the fixed bases. If this residue 
after ignition colors moistened turmeric paper brown, we may 

* See Fl. Heller in s. ArcMv, 1845, page 1, and W. Moore, Dublin Quarterly 
Journal, 1854, March. 



536 SEMIOLOGY OF HUMAN URINE. 

conclude tliat it contains potassium or sodium — the latter may 
be recognized by the yellow color which it imparts to the blow- 
pipe flame. Magnesium and calcium remain behind as carbo- 
nates, when the residue has not been ignited too strongly, and 
are not, therefore, soluble in water, but dissolve in the dilute 
acids. If phosphate of sodium and ammonic hydrate are added 
to this solution, the calcium and magesium are precipitated as 
ammonio-magnesian and calcic phosphates. These two sub- 
stances may then be separated from each other in the manner 
to be described below. 

Calcic oxalate blackens on ignition on account of the combus- 
tion of the organic substances, but on being further ignited it 
readily becomes white and does not fuse. If strongly ignited, 
quick-lime is formed, which turns moistened turmeric paper 
brown. If gently ignited only calcic carbonate is formed which 
dissolves in hydrochloric acid with effervescence. If this solu- 
tion is neutralized with ammonia no precipitate results, until 
oxalic acid is added, when calcic oxalate is again precipitated, 
and shows under the microscope its characteristic crystalline 
form. (See § 45, B.) The calcic oxalate is insoluble in boiling 
water and potassic hydrate ; it is soluble in hydrochloric acid 
without effervescence. 

Calculi of calcic oxalate are tolerably frequent, especially in 
children. They are either small, pale, and smooth — hemp-seed 
calculi — or are larger, of rough exterior, tuberculated, warty and 
colored on the surface, usually dark brownish or even blackish 
— mulberry calculi. These latter, by their rough exterior, usually 
irritate the urinary passages very much, and give rise to severe 
disease (inflammation, hemorrhage). 

Calculi formed of calcic carhonate alone or containing it as 
the principal constituent are quite rare. They occur usually 
in large numbers in the same individual, have a whitish gray 
(rarely a dark, yellowish, or brownish) color, and usually pre- 
sent an earthy, chalky a23pearance. Their formation shows a 
lack of phosphoric acid in the urine. More frequently calcic 
carbonate occurs as a subordinate constituent of other calculi, 
mixed with calcic oxalate or the earthy phosphates. 

Calculi of calcic carbonate blacken on ignition, since they 
usually contain a considerable amount of organic matter (mu- 
cus), but they easily burn white and are infusible. The residue 
after ignition has the same properties as that of calcic oxalate 



URINARY CALCULI AND OTHER CONCRETIONS. 537 

calculi; it either remains calcic carbonate or is changed by 
strong ignition into quick-lime. 

The very characteristic property of this calculus of dissolv- 
ing in hydrochloric acid luitli effervescence renders its detection 
easy. 

Ammonio-magnesian jjJiospJiate and (basic) calcic phosphate ordi- 
narily occur mixed together as constituents of the same urinary 
concretion. Such calculi of the earthy phosphates indicate 
that the urine has for a long time been ammoniacal on account 
of the decomposition of urea within the urinary passages. They 
may reach a considerable size ; they have usually a whitish 
color, and are more soft, porous, and chalky if the ammonio- 
magnesian phosphate predominates, or denser and harder if 
the calcic phosphate predominates. 

Chemically they have the following characteristics : They do 
not char on being ignited, but melt to a white enamel-like mass, 
whence they have received the name oi fusible calculi. Also, 
after strong ignition they do not have an alkaline reaction, 
whereby they may be distinguished from calculi of calcic oxalate 
and carbonate. They are soluble in hydrochloric acid, without 
effervescence both before and after ignition, and the hydro- 
chloric acid solution of the ignited powder is precipitated by 
ammonia. 

In order to separate these two constituents, the calcic and 
ammonio-magnesian phosphates, from each other, the ignited 
powder should be dissolved in dilute hydrochloric acid, and fil- 
tered. Ammonia is then added to the filtrate until the reaction 
is only very feebly acid, or the filtrate neutralized completely 
with ammonia until a turbidity appears, which is dissolved with 
a few drops of acetic acid. If oxalate of ammonium is now 
added, the calcium only will be precipitated as oxalate, while 
the ammonio-magnesian phosphate will remain in solution, and 
after filtering off the calcium precipitate may be obtained by 
saturating the filtrate with ammonia. 

Calculi of neutral calcic phosphate resemble, in their physical 
and chemical properties, those of the earthy phosphates, but 
differ from them in not containing magnesium, so that their 
hydrochloric acid solution, after the precipitation of the calcium 
with ammonic oxalate, gives no further precipitate by saturating 
with ammonia. Such calculi are quite rarely seen. But ac- 
cording to my experience the occurrence of gravel, at least, 



538 SEMIOLOGY OF HUMAN URINE, 

composed of calcic pliospliate, is mucli more frequent than was 
formerly supposed, and I have observed a large number of such 
cases. I wish here to lay stress upon this observation, since 
the practising physician in most of these cases, without making 
an accurate examination of the gravel, considers it to consist of 
uric acid, and thereupon orders the use of alkalies, Vichy waters, 
etc., — a procedure which, in these cases, instead of benefiting, 
only increases the evil. 

Calculi do not always, however, have so simple a composi- 
tion as those hitherto considered. Sometimes they contain 
several constituents. Thus there are calculi which consist of a 
mixture of uric acid and urates with the earthy phosphates ; 
others which are mixtures of calcic oxalate and the phosphates. 
Calculi have been found, even, which contained at the same 
time uric acid, urate of ammonium, calcic oxalate, calcic phos- 
phate, calcic carbonate, and ammonio-magnesian phosphate, six 
different constituents, therefore. These different constituents 
are sometimes mixed intimately with each other, and some- 
times are deposited upon each other in different layers, which 
have evidently been formed at different times. This is explained 
by the fact that different sediments are deposited in the urine 
of the same patient at different times, and these adhere to any 
calculus present and increase its size. Thus, alternate layers 
of uric acid and urates occur, if in a case of long-continued urate 
diathesis the urine is sometimes strongly acid, so that the urates 
are decomposed, and uric acid itself is deposited, and some- 
times slightly acid or neutral, so that the undecomposed urates 
are deposited upon the calculus. If the uric acid diathesis al- 
ternates with the oxalic acid, then alternate layers of uric acid 
and calcic oxalate are formed. Calculi very frequently met with, 
which consist of alternate layers of uric acid or calcic oxalate 
and the earthy phosphates, occur when the uric or oxalic acid 
diatheses periodically subside, and the urine becomes alkaline 
in the interval from the decomposition of urea, to which the 
abundant separation of mucus from the irritation of the calculus 
or the retention of urine, which sometimes occurs from the ob- 
struction of the urethra or the exit of the bladder, contribute. 
The alternate layers of uric acid and calcic phosphate in a cal- 
culus are sometimes caused artificially by drugs, if the patient 
takes alkalies to antagonize the uric acid diathesis, since these 



UBINARY CALCULI AND OTHER CONCRETIONS. 539 

render the urine alkaline and cause a deposition of calcic phos- 
phate which adheres to the calculus. 

Most calculi have a nucleus which is sometimes a foreign 
body, upon which the urinary sediments deposit and form a 
crust. Every foreign body, which has in any way gotten into the 
urinary passages from without, or has been formed within the 
same, such as fibrine, or blood coagula, or clumps of mucus, 
may thus become the nucleus of a calculus. Retained gravel 
may also form the nucleus of a calculus. In the latter case 
the nucleus sometimes has a different chemical composition 
from the rest of the calculus, if during the formation of the 
latter the character of the sediment becomes changed. Some- 
times it happens that a calculus has, instead of a nucleus, a 
vacant space in its interior; in this case, the nucleus consisted 
of mucus which later became dry. In rare cases it is noticed 
that the nucleus rattles within the stone, which is to be ex- 
plained in the same way by the drying up of the mucus. Some- 
times the calculus is made up of gravel or several small stones, 
which are united by a cement, and which sometimes have the 
same chemical composition as the calculus and sometimes a 
different one. All of these conditions must be taken into con- 
sideration when the chemical composition of the concretion is 
to be determined, and from this conclusions are to be drawn as 
to the probable processes which take place in its formation. 

False urinary concretions also occur, and their recognition 
is of especial importance to the practising physician, when a 
hypochondriacal patient is brought to him laboring under the 
tormenting idea that he is suffering with a calculus or gravel. 
Thus it happens sometimes that sand or small stones, which 
accidentally get into the chamber-vessel, or are left in it after 
scouring it, are considered to be urinary concretions. They con- 
sist usually of silica, and may be distinguished from urinary 
concretions by their appearance and physical properties (great 
hardness), and if necessary by a chemical analysis by which both 
an absence of the characteristic properties of those substances 
which form urinary calculi is revealed, and upon analysis (ig- 
nition with sodio-potassic carbonate, and further treatment ac- 
cording to § 20) a considerable amount of silicic acid is detected 
in them, which is not found in true urinary concretions or only 
in traces. 



DESCEIPTION OF THE PLATES. 

PLATE I., PLATE II., AND PLATE III., FIG. 1-4, FROM DR. FUNKE'S 
PHYSIOLOGICAL ATLAS. 

Plate I. 

Fig. 1. Hippuric Acid, prepared from normal human urine, 
recrystallized from water. 

In addition to the ordinary prisms there are frequently 
formed, especially upon slow separation of the hippuric acid, 
crystals which are precisely similar to those of triple phos- 
phate ; such crystals are figured in the left lower third of the 
figure. 

Fig. 2. Uric Acid of different forms, partly prepared by dis- 
solving and re crystallizing chemically pure uric acid, partly by 
treating sediments of urates with acids, and partly by its spon- 
taneous separation from the urine as a sediment. 

The numerous forms of uric acid, from the simple rhom- 
bic plates with rounded obtuse angles most frequently seen to 
the rarer modifications, are easy to comprehend from the figure. 
The dumb-bells, shown in the left upper part of the figure, were 
artificially prepared, but they sometimes occur in spontaneous 
urinary sediments. Eunke has always obtained them when he 
dissolved chemically pure uric acid in potassic hydrate, and 
precipitated it again under the microscope by concentrated 
hydrochloric acid. 

Fig. 3. Urinary Sediment of uric acid, urate of sodium, and 
calcic oxalate, from the urine of a typhoid convalescent. 

A common form of uric acid crystals in sediments consists 
of the figured, large, thick clumjDS united by twos at their base, 
which are made up of numerous, long, small, Avhetstone-shaped 
crystals, and which, as a rule, appear colorless. The beautiful, 
glittering, envelope-shaped crystals are calcic oxalate. The 
small, round, and angular dark granules, which are partly single 
and partly lie together in irregular groups and heaps, consist of 
urate of sodium which always appears in the urine in this mole- 
cular form. (Compare Plate II., fig. 1 and 2.) 

Fig. 4 Urinary Sediment with epithelial casts and numerous 

540 



DESCRIPTION OF PLATES. 541 

epithelial cells, taken after death with a catheter from the 
bladder of a patient who had died from typhoid fever. 

The cylindrical casts figured consist of the epithelial lining 
of Bellini's tubes, whose round nucleated cells are plainly visi- 
ble through a finely granular mass. The keel-shaped, caudate, 
and spindle-shaped cells which lie free come from the ureters 
and pelves and calices of the kidney. 

Fig. 5. Urinary Sediment of hyaline tubular bodies, bladder 
epithelium, and mucous corpuscles, from a patient with acute 
miliary tuberculosis. 

These casts, which are somewhat rarer than the foregoing, 
are so hyaline and homogeneous, that it is only with care that 
they can be distinguished from the surrounding fluid. In the 
case shown they are in places rendered more plainly visible 
by being filled with small granules of urate of sodium ; their 
ends are sometimes swollen like a knob. Near them are seen 
roundish, long or polygonal, pavement epithelial cells from the 
bladder, most of which are plainly nucleated, and very granular 
mucous corpuscles. 

Fig. 6. Urinary Sediment consisting of fibrinous casts, blood 
and pus corpuscles, and epithelial cells ; albuminous urine of a 
typhoid patient, in whom the section showed a considerable in- 
flammatory infiltration of the cortical substance of the kidneys. 

The granular cylindrical bodies formed from an apparently 
granular molecular mass are coagula of fibrine (croupous exuda- 
tion) from Bellini's tubes, whose form they have retained. Some 
contain blood and pus corpuscles enclosed in them, but these 
are seen in considerable amount free, the blood globules mostly 
swollen up like a little bladder, but partly with the central de- 
pression still plainly perceptible. The bipolar epithelial cells 
have already been described in connection with fig. 4. 

Plate II. 

Fig. 1. Urinary Sediment of urate of sodium from the heavy 
morning urine of a tuberculous patient. 

The ordinary whitish, yellowish, or brick-colored deposit, 
which settles from a concentrated acid' urine (especially in fe- 
vers) after cooling, consists almost exclusively of sodium urate, 
which separates in the form of granular molecviles. When 
separated rapidly these granules are very fine and usually 
clumped together in the mossy groups shown in the figure. 



542 BESCBIPTION OF PLATES. 

Between these may be seen, when the urine has stood for some 
time (fig. 4), a few fermentation spores, and (at the right lower 
edge) sometimes bladder epithelial cells which are usually very 
granular and appear wrinkled. 

Fig. 2. Urinary Sediment consisting of urate of sodium, phos- 
phates, and mucous coagula, after three days' standing. 

The sodium urate has in this case .separated in much larger 
darker granules and in larger heaps than in the previous figure. 
The uniformly granular membrane-like forms shown in the 
centre of the figure are fragments of the film consisting of the 
amorphous earthy phosphates with which urine undergoing de- 
composition exposed to the air is often covered. The smaller 
and broader curved bands, which consist of exceedingly fine 
dots and granules arranged in rows, are mucous coagula, which 
are frequently found in acid urine and may be easily con- 
founded with the casts above mentioned. In addition fermen- 
tation spores may be found here also partly arranged in rows 
and plates (as at the lower edge), and single very granular mu- 
cous cor23uscles. 

Fig. 3. Urinary Sediment consisting of triple phosphate and 
numerous mucous corpuscles, from the freshly passed alkaline 
urine of a patient with catarrh of the bladder. 

The crystals of ammonio-magnesian phosphate have different 
forms, but they are always easy to recognize without crystallo- 
graphical or chemical analysis. The mucous corpuscles are 
rather small, much contracted, and granular, and usually with 
their edges united so as to form large groups like a coat of mail 

Fig. 4 Urinary Sediment consisting of urate of sodium, uric 
acid, and fermentation spores, from a urine undergoing acid fer- 
mentation after standing. 

Every normal and almost every acid pathological urine under- 
goes acid fermentation upon long standing. "With the increase 
of the acid reaction there form in it the small nucleated fermen- 
tation sjDores, which increase by budding, and thus form simple 
and branching rows like those shown. At the same time the 
yellow uric acid crystals of the simple forms shown in the figure 
separate in gradually increasing amount from the urate of so- 
dium which is present in the ordinary form. In addition to 
these, small octahedral crystals of calcic oxalate frequently ap- 
pear (as, for example, at the right upper edge). 

Fig. 5. Urinary Sediment consisting of triple phosphate crys- 



DESCRIPTION OF PLATES. 043 

tals and urate of ammonium, from a urine which has under- 
gone alkaline fermentation in a case of paralysis of the lower 
extremities in consequence of a spinal affection. 

The triple phosjohate crystals figured have the most common 
form which occurs in every decomposed urine. The urate of 
ammonium separates at first in the form of very fine molecules, 
from which the gradually increasing, dark, strongly refracting 
globules develop, which are later covered with fine spiculse of 
varying length, like a thorn apple 

Fig. 6. Nitrate of Urea precij)itated from very concentrated 
human urine by nitric acid. 

Plate III. 

Fig. 1. Urinarij Sediment consisting of uric acid crystals, from 
the urine of a girl suffering with acute rheumatism (during the 
menstrual period). 

In addition to the yellowish - brown rhombic tables, kegs, 
whetstones, etc., of uric acid, which are mostly united together 
in groups and bunches, and represent the most common forms 
of sediment so frequently seen in the shape of a golden, glitter- 
ing, granular sand, there are numerous distinctly yellow blood 
corpuscles, which are swollen, bladder-shaped, and of very dif- 
ferent size. 

Fig. 2. Human Blood Corpuscles treated with water. 

The gradual change produced in blood corpuscles is shown 
in the figure beginning at the left and increasing toward the 
right. The first result of the action of water is that the cells 
swell up, become more lenticular and finally spherical, while 
the central depression becomes more nearly level and is finally 
arched; this is necessarily accompanied by a shortening of 
the transverse diameter of the disk. They appear, therefore, 
smaller, and the shadow in the centre grows pale and disap- 
pears, and the more a spherical shadow on the edge appears, the 
less clearly does the cell standing upon its edge show the lenti- 
cular shape. By the further action of the water the cells be- 
come fainter and paler, and more difficult to distinguish from 
the surrounding fluid, since their contents, by the imbibition of 
water, obtain the same refracting power as the external fluid ; 
they appear only as exceedingly delicate hyaline bladders, and 
finally become totally invisible. If a concentrated solution of a 
neutral salt is then added, they appear in the distorted, angu- 



544 DESCRIPTION OF PLATES. 

lar, and ragged forms seen in the lower riglit-liand corner of 
the figure. 

Fig. 3. Pus Corpuscles, 

The lower half of the figure shows the normal pus corpuscles 
as round, pale, delicate, granular bladders of somewhat varying 
size, of which some permit a single round eccentric nucleus to 
be seen, but others a nucleus several times divided. As the 
figure shows, some of the corpuscles are very distinctly limited 
by sharp lines, while others show only a delicate contour as if 
washed. The upper half of the figure shows the action of acetic 
acid upon the pus corpuscles. They swell up and their surface 
becomes smooth and so hyaline that the contour can sometimes 
no longer be distinguished ; thereby the nuclei of different num- 
ber and form become visible, partly as single round elongated, 
biscuit or horseshoe-shaped bodies, and partly double or triple 
and quadruple in the different forms and grouping as shown in 
the figure, as if they were formed by splitting of the single ones. 

Fig. 4. Cystin, obtained from a vesical calculus, and recrys- 
tallized from ammonic hydrate. 

Fig. 5 and 6 illustrate the most important and most fre- 
quently occurring organized elements which are found in the 
urinary sediment in cases of cancer of the bladder. 

For the special explanation of the individual figures and their 
importance consult § 115. 

Plate IY. 
VogeVs Urinary Color Table. 

Fig. 1. Pale yellow. Fig. 6. Eed. 

*•' 2. Light yellow. *^ 7. Brownish red. 

'' 3. Yellow. '' 8. Keddish brown. 

" 4. Keddish yellow. '^ 9. Brownish black. 
'' 5. Yellowish red. 

Hsematin in acid alcoholic solution shows, in addition to the 
two absorption bands between C and D, figured in Plate IY., 
when moderately diluted, two others which are feeble, disap- 
pear more quickly on further dilution, and are, therefore, not 
characteristic. 

Methsemoglobin shows, when the solution is not alkaline, the 
same absorption bands as hsematin. (Page 181.) 

The spectrum of oxyhgemoglobin shows the two very charac- 
teristic absorption bands described on page 179. 



ibauerandVogel.iViialysis of Urine 7'^ Edition. Plate i. 

Egl. Tig.^. 




Fig. 3. 




Jig. 5. 





Eg. 6. 




)auerand\'bgel, Analysis of ITrme 7'1* Edition 



I'late 




Fig. 2. 




Fig. 4 




Jig. 6. 




iil)auerand\ogel,Aiialvsis of TTriiie 7'^ Edition. 



Plate 3 




Fig. 2. 




Fig. 3. 



Fig. 4. 





Fig. 5 



Fig. 6. 




iiier 



•andYogel, Analysis of Urine 7^^ Edition. 



Plate 4 




ZBmntish-red.. SReddishimm. 9BmmishNach. 

Table of colors of the Urine. 



^ 



t^ 



INDEX, 



Abtetic Acid, 200. 

Abnormal Constituents of Urine, 91. 

" " " " Accidental, 

190, 406. 
" " " " Siijnifican ce 

of, 378. 
Acetamld, Elimination of, 208. 

" Influence of upon the Estimation of 

Urea, 241. 
Acetate of Sodium, Standard Solution of, 252. 
Acetic Acid, 135. 

" " Action of upon Pus Corpuscles, 
183. 
Acetone, 157. 
Acid, Abie tic, 200. 

" Amidobenzoic, 199. 
'• Amidosuccinaminic, 200. 
" '' Decomposition of 

Avhen ingested, 209. 
" Anisic, 51, 199. 
" A-sparagic, 4, 12. 
" Baldrianic, 137. 
" Benzoglycholic, 51. 
" Benzoic, 1.38. 
" " Elimination of when in<rested, 

198. 
" Benzoic, Formation of from Hippuric 

Acid, 50. 
" Butyric, 136. 
" Camphoric, 200. 
" Carbamic, 206. 
" Carbolic, 55, 201. 
" " as cause of dark-colored Urine, 

74, 369. 
'• Carbonic, in Disease. 517. 
" " Quantitative Estimation of, 312. 

" Chlorobenzoic, 199. 
" Cholic, 124, 398. 
" Choloidic, 51, 398. 
" Cholonic, 399. 
" Cinnamic, 198. 
" Cumarinic. 199. 
" Cnminic, 199, 203. 
" Damaluric. 57. 
" Damolic, 57. 
" Ethyldiacetic, 1.57. 
" Formic, 134. 
" Glycocholic, 125. 
" Hippuric, 47. 
'• " as a Sediment. 414. 

" nvdrochloric, Standard Solution of, 299. 
" Hydurilic, 39. 
'^ Kinic, 48, 51. 
" Kryptophanic, 74. 
" Lactic, 130. 

" " Significance of, 517. 
" Mandelic, 198. 
" Mesitylenic, 203. 
" Mesitvlenuric, 203. 
" Methylliydantoic. 20G. 
" Nitric, Test for Albumen, 96, 379. 

35 



Acid, Nitrobenzoic, 199. 

" Omicholic, 66. 

" Oxalic, Quantitative Estimation of, 321. 

" " Standard Solution of, 256. 

" Oxaluric, 42. 

" Oxy benzoic, 199. 

" Oxymandel, 153. 

" " Significance of, 517. 

" Oxyphenic, 165. 

" Paralactic, 131. 

'• Paranitrobenzoic, 203. 

" Paranitrohippuric, 203. 

" Paraoxyber.zoic, 60, 199. 

" Phenylic, 55, 74, 201. 

" Phosphoric, Analyses, 349. 

" '• in Pieces, 508. 

" " Influence of disease upon, 

509. 

" - " Quantitative Estimation of, 

250. 

" " Significance of, 504. 

" " Standard So'utiou of, 252. 

" Phthalic, 51, 199. 

" Picric, 51. 

'' Propionic. 135. 

" Propyl benzoic, 203. 

" Pvrogallic. 200. 

" Quimc, 198. 

" Salicylic, 199,208. 

" SMlicyluric, 51. 

" Silicic, 88. 

" Succinic, 52, 200. 

" Siilphamic, 206. 

" Sulphindigotic, 72. 

" Sulphuric, Analyses, 349. 

" " Influence of Disease upon, 503. 

" '* Quantitative Estimation of, 

:^57. 
" " Significance of, 497. 

" Standard Solution of, 306, 314. 

" Tannic, 200. 

" Tam-ocarbamic, 207. 

" Taurocholic, 124. 

" Taurylic, 57. 

" Toinic, 199. 

" Uiate of Ammonium, 164. 
" " " Calcium, 165. 

" " " Potassium. 164. 

" " " Sodium, 161. 

" Uric, 35. 

" '• as a Sediment, 162. 
" " " " Significance of, 410. 

>' in Calculi, 533. 
" " Influence of Disease upon, 482. 
" " Quantitative Estimation of, 287. 

" " Significance of, 481. 

" Urochloralic, 201. 

" Xanthoproteic, 92. 
Acidity of Urine, Estimation of, 256. 
Acids, Biliary, 124, 318, 398. 

" Fatty, 134. 



545 



546 



IJS'DEX. 



Acids, Free, Significance of. 484. 
'^ Mineral, m Urine, 196. 
'•• Organic, " " 19S. 
Acute Febrile Diseases, Amount of Urine in, 

451. 
Acute Febrile Diseases, Amount of Chlorine in, 

493. 
Acute Febrile Diseases, Amount of Coloring 

Matters in. 464. 
Acute Febrile Disease?, Amount of Solids in, 

456. 
Acute Febrile Diseases, Amount of Urea in, 

477. 
Acute Nepliritis, Case of, 525. 

'• YelU)W Atrophy of the Liver, 4, 131, 153. 
Addison's Disease, Amount of Indican in, 307. 
Air Bath, 216. 
Albumen, 291. 

" Analyses, 351. 
" Approximate estimation of, 387. 

" Detection of, 95. 

" Q,uantirative Estimation of, Gravi- 

metric, 293. 
'' Quantitative Estimation of, by Bo- 

deker's Metliod, 297. 
" Quantitative Estimatiou of, by Cir- 

cuinpolarization. 296. 
" Quantitative Estimaticm of, by Dif- 

ference in Sp. Gr., 25*7. 
" Quantitative Estimaiion of, by Gir- 

geiisohn's Method. 299. 
" Quantitative Estimation of, by Libo- 

rius-s Method, 298. 
" Quantitative E s r i ni at i o n of, by 

Mehu's Method, 298. 
" Quantitative Estimation of, by Yo- 

gePs Optical Method, 297. 
" Significance of, 379. 

All)uminose, 98. 
Albuminuria, 381. 
Alcohol, 1.57. 

'• Elimination of when ingested. 200. 
Alkalies, Action of on Pus Corpuscles, 184. 
Alkaline Carbonates, 196, 408. 
Salts, 196. 
" Earths, 198. 
" Reaction of Urine, 377. 
Alkanet, Elimination of when ingested, 200. 
Alkapton, 114. 
AUantoin, 144. 

" Decomposition of when ingested, 

206. 
" Influence of upon the Estimatiou of 

Urea, 241. 
" Significance of, 517. 
Alloxan, 13, 146. 

Formation of from Uric Acid, 39. 
Alloxantin, Decomposition of when ingested, 

206. 
Alloxantin, Formation of from Uric Acid, 39. 
AmJdobenzoic Acid, 199. 
Amidosuccinaininic Acid, 200, 209. 
Ammonia Analyses. 352. 

Quantitative Estimation of, 306, 308. 
" Significance of, 486. 

Ammonio-matrnesian Phosphate, 168. 

" "" '' in Calculi, 

537. 
Ammonium Chloride, 4, 12. 

Salts in Urine, 86, 196. 
Urate, Acid, 164. 
Amount of Urine, Quantitative Estimation of. 
210. 
" " '* Significance of, 444. 
" " " Variation in Disease, 451. 
Ampelopsis Hederacea, 1,56. 
Amphigenous Reaction of Urine, .371. . 
Amphoterous Reaction of Urine, 371. 
Amygdalin, Elimination of when ingested, 208. 
Analytical Experiments, 347. 
Anilin, 206. 



Anisic Acid, 51, 199. 

Antimony in Urine, 408. 

Apparatus for Quantitative Analysis of Urine, 

226. 
Appendix — Examination of Calculi, 531. 
Approximate Quantitative Estimations, 344. 
Arieotneters. 211. 
Arsenic in Urine, 408. 
Arseniuretted Hydrogen, 74. 

" " H fem ogl o bin i n 

Urine, 392. 
Asparagic Acid, 4, 12. 
Asparagin, 4, 12. 

" Elimination of when ingested, 209. 

Assafcetida, Elimination of when ingested, 209. 

Bacteria in Urine, 188. 
Balance, Mohr-Westphal, 213. 
Baldrianic Acid, 137. 
Balsam Copaiba, 96. 
Barium Butyrate, 136. 

Chloride, Standard Solution of, 258. 

" Salts in Urine. 198. 
Baryta Solution for Urea Estimations, 235. 
Bases, Organic in Unne, 204. 
Benzoglycolic Acid. 51. 
Benzoic Acid, 50, 138, 198. 
Benzoic Ether, 198. 
Benzol, 202. 

Benzol Series of Organic Compounds, 202. 
Benzol-sulphate of Sodium. 204. 
Bilberries. Influence of upon the Urine when 

ingested. 209. 
Biliary Acid-, 124. 

'• " Detection of in Urine, 127. 

Pettenkofer's Test for, 12';. 

" " Quantitative Estimation of, 318. 

" Significance of, 398. 

" Co'oring Matters, 118. 

" " " Detection of in Urine, 

121. 

" " " Significance of, 398. 

" Constituents, 117. 
Bilifuscin, 121. 
Biliprasin, 120. 
Bilirubin. 118. 
Biliverdin, 120. 
Bismuth Test for Sugar, 106. 
Bitter Almond Oil, 198. 
Black Urine. 74. 
Bladder, Cancer of— Case, .529. 
" Epithelium of, 427. 
" Hypera?mia of, .390. 
" Inflammation of, 429. 
Blenorrhoea, 429. 
Blood in Urine, 178. 

Siirnficance of, 389, 437. 
Blood Pigment in Urine, 179. 

" Significance of, 392. 
Blue Urine, 367. 

BiJdeker s Method of Estimating Albumen, 297. 
Bodo Urinarius, 188, 438. 
Bottger's Test for Sugar, 106. 
Brenzcaiechiii. 155. 
Bromide of Potassium, 197. 
Bunsen's Method of Estimating Urea, ^44. 
Burette, 229. 
Butyrate of Barium, 136. 
Butyric Acid, 136. 

Cadmium in Urine. 195. 
Calcic Carbonate Calculi, 536. 

" Lactate, 1.32. 

*' Oxalate, in Sediment. 165. 

" " Approximate Estimation of, 340. 

" " Calculi. 536. 

" " Significance of, 418. 

" Salts in Urine, 198. 

" Urate, 165. 

" Phosphate, S3. 

Calculi, 537. 
Calcium Analyses, 351. 



mDEX. 



547 



Calcium, Qiaantitative Estimation of, 299. 

" " Gravimet- 

ric, 301. 
" Significance of, 511. 
Calculi, Exalniination of, 531. 
Camphor, Elimination of when ingested, 209. 
Camphorcymol, 203. 
Camphoric Acid, 200. 
Cancer of Bladder, Case of, 529. 
Cancerous Masses in Urine, 430. 
Carbamate of Ammonium, 14. 
Carbamic Acid, i!06. 
Carbolic Acid, 55, 201, 408. 

Cause of Dark Trine, 74, 369. 
Carbonic Acid, Qiumtitative Estimation of, 312. 

" " Significance of, 517. 

Cam in, 34. 
Casein, 98. 
Casts in Sediment, 185. 

" " Significance of, 434. 

Chemical Properties of Normal Urine, 3. 
Reaction of Normal Urine. 6. 
" " " Urine in Disease, 370. 

Chloral, Elimination of, 201. 
Chloride of Ammonium, 4, 12. 

Barium, Standard Solution of, 258. 
" Potassium, 79. 

" Sodium, 76. 

Chlorine Analyses, 348. 
" in Disease, 493. 
" Quantirative Estimation of, 245. 
" Significance of, 489. 
Chlorobenzoic Acid, 199. 
Chloroform, Elimination of, 201, 408. 

" as a Cause of Albuminuria, 384. 

Cholepyrrhin, 118. 
Choletelin, 119. 
Cholesterin. 130 
Cliolic Acid, 124, 398. 
Choloidic Acid, 51, 398. 
Cholonic Acid, 399. 

Chronic Diseases, Amount of Urine in, 452. 
" Solids in, 458. 
" " " " Chlorine in, 496. 

Chylous Urine, 140. 
Chyluria, 3'.)7. 
Cinnamic Acid, 198. 

Cirrhosis of the Liver, Urophsein in, 365. 
Coagulable Urine, 388. 
Cobalt in Urine, 408. 
Cochineal. Elimination of. 209. 
Coloring Matters, Elimination of, 209. 
Coloi-ing Matter of Urine, Normal, 363. 
" " " Abnormal, 365. 

" " "• Accidental, 368. 

" '• " Quantitative Estima- 

tion of, 222. 
" " " Significance of, 461. 

Bile, 118, 121, 398. 
Blood, 179, 392. 
Concluding Observations, 518. 
Constituents of the Bile in Urine. 117. 
" " Urine, Normal, 11. 

'« " " Abnormal, 91, 378. 

" " " Accidental, 190, 406. 

Copaiba. 96 
Copper in Urine, 407. 

Creosote Solution for Preserving Sediments, 335. 
Cumarinic Acid. 199. 
Cuminic Acid, 199, 203. 
Cupric Sulphate, Standard Solution of, 261. 
Cyanate of Ammonium, 13, 
Cystin, 171. 

Si^diment. Significance of, 423. 
Calculi, 534. 

• 
Damaluktc Acid, 57. 
Damolic Acid, .57. 
Dark-colored Urine, 223. 
" " " Caused by Tar and Car- 

bolic Acid, 74, 369. 



Desiccator, 217. 
Diabetes, 445, 

" Insipidus, 4.56. 

" *' Case of, 519. 

" Mellitus, 101, 403. 

Mellitus, Case of, 518. 
Diabetic Sugar, 101. 
Dioxindol, 69, 209. 
Distomum Hiematobium, 441. 
Donne's Pus Test, 184. 

Earthy Phosphates, 83. 

" " as a Sediment, 168, 416. 

" " Approximate Es-timiition 

of, 344. 
" " Indirect Estimation of, 

304. 
" " Quantitative Estimation 

of, 299. 
" " Significance of, 511. 

" " in Disease, 514. 

Ecchinococcus Cysts in the Sediment, 440. 
J^^mpyreumatic Oils, Elimination of, 209. 
Entozoa in the Sediment, 440. 
Epithelial Casts in the Sediment, 434. 
Cells " '• 1T7. 

" " " " Significance 

of, 425. 
Estimations, Approximate, 344. 
Quantitative, 210. 
Ether, Elimination of, 209. 

" Benzoic, 198. 
Ethereal Sulphates of Sodium, 204. 
Ethyldiacetic Acid, 157. 

F.^CEs, Phosphoric Acid in, 508. 
Farrant's Fluid for Preserving Sediments, 385. 
Fat in Urine, 140. 
" " Quantitative Estimation of, 318. 

" " Quantitative Estimation of, by 

Kletzinsky's Method, 396. 
Significance of, 395. 
Fntty Acids, 134. 

'• " Detection of in Urine, 137. 

Febrile Diseases, Amount of Chlorine in, 493. 
" " " Pigments in, 464. 

" " " Solids in, 456. 

" " " Urea in, 477. 

" Urine in, 451. 

Fehling's Copper Solution, 262. 
Fehiing's Method of Estimating Sugar, 261. 
Fermentation of Urine, 7, 159. 

" Quantitative Estimation of Su- 

gar by, 276. 
" Spores in the Sediment, 188. 

Test for Sugar, 104. 
Ferrocyanide of Potassium, 196. 

" " " Standard Solution 

of, 286. 
Fibrine in Urine, 97. 

" Significance of, 388. 
Fibrine Calculi, 534. 
Filaria immitis in Chyluria, 442. 
Food, Influence of on the Amount of Urea. 476. 

" " " " " Urine, 4. 

Formic Acid, 134. 
Free Acids, Test for, 6. 
Fungi in Urine, 187. 

'•" " •' Significance of, 437. 
Fusible Calculi, 537. 

Galacturia, 397. 

Gamboge. F.limination of. 209. 

Garlic, Elimination of, 209. 

Girgensohn's Method of Estimating Albumen, 

299. 
Glycerine Solution for Preserving Sediments, 

ass. 

Glycocholic Acid, 12.5. 
Glycocoll, 4. 39, 50, 125. 

Elimination of, 206. 
Glycosuria, 101, 400. 



548 



INDEX. 



Gmelin's Test for the Biliary Pigments, 121. 
Golden Sulphur, Elimination of, 501. 
Gonorrhoea, Urine in, 429. 
Graduated Burettes, 229. 
Cylinders, 229. 
" Pipettes, 226. 

Granular Casts. 434. 
Grape Sugar, 101. 

" *' Analyses, 350. 

" *' Approximate Estimation of, 402. 

" " Quantitative *• " 261. 

" " Significance of, 400. 

Green Urine, 367. 
Guanin, 13. 

Elimination of, 206. 

H^MATOCKYSTALLIN, 179. 

Haematoidin, 118. 
Hsematuria, 178, 389, 437. 
Case of, 5-28. 
Hffimin Crystals, 182. 
Hsemoglobin, 179. 

Significance of, 392. 
" Ti'ansformatiou of to Urobilin, 

64, 464. 
Hsemoglobiiiuria, 392. 

Case of , 527. 
HiBmorrhoids, Vesical. 390. 
Heart Disease, Case of, 520. 
Heller's Test for Albumen, 96. 

'• " Urophsein, 365. 

Hippuric Acid, 47. 

'• Sediment, Sii,niificance of, 414. 
Hilger's Method of Estimating Iodine, 282. 
Hormisciuin sacchari, 439. 
Hiifner's Method of Estimating Urea, 242. 
Hyaline Casts, 435. 
Hydrate of Sodium, Standard Solution of, 256, 

300, 307, 314. 
Hydrobilirubin (Urobilin), 63. 

" Foimation of from Htemoglob- 

uliii 04, 464. 
Hydrochloric Acid, Standard Solution of, 299. 
Hydrogen Peroxide, 89. 
Sulphide, 142. 
Hydruria, 457. 

Case of, 520. 
Hydurilic Acid, 39. 
Hyperaemia of the Bladder, .390. 
Hypobromite of Sodium, 16. 

" " " Staudard Solution of, 

242. 
H5^pochlorite of Sodium, 16. 
H^^poxanthin (Sarkiu), 33. 

" in the Sediment, 174. 

" " " Significance of, 

425. 

Indican, 67. 

" Quantitative Estimation by Jaffe's 

Method, 319. 
" in Disease, 366. 
Indigo, 51. 

" Elimination of, when ingested, 209. 

Blue, 68. 
" " in Disease, 367. 

Red, 65, 68. 
" " in Disease, ,367. 

Indigrubin, 65, 68. 

" in Disease, 367. 

Iiidol, 67. 

Elimination of after subcutaneous in- 
jection, 209. 
Infusoria, 187. 

" Significance of, 437. 

Inorganic Constituents of Urine, 76. 
Inosite, 114. 

" Significance of, 405. 
Intestinal Obstruction, Indican in, 366. 
Iodide of Potassium, 197. 

•' " " Standard Solution of, 279. 



Iodine, Colorimetric Estimation of, 283. 

'' Quantitative Estimation of, byHilger's 

Method, 282. 
'• Quantitative Estimation of by Kerst- 
ing's Method. 278. 
lodoquinine Sulphate, 205. 
Iron in Urine, 84. 

" Quantitative Estimation of, 285. 
Isatin, 51. 69. 

Elimination of when ingested, 209. 
Isoalloxanate of Ammonium, 40. 

Jaffe's Method of Estimating Indican, 319. 

Kersting's Method of Estimating Iodine, 278. 
Kidnev, Ca^ts fnnn, 185, 434. 
Epithelium of, 427. 

" Suppuration of, 429. 
Kinic Acid, 48, 51. 

Knapp's Method of Estimating Sugar, 265. 
Knop-Hiifner's Method of Estimating Urea, 

242. 
Kreatin, 13, 25. 
Kreatinin, 19. 

" Analyses, 351. 

" Quantitative Estimation of, 291. 

" Significance of, 515. 

Krj'ptophanic Acid, 74. 
Kyesteine, 437. 

Lactate of Calcium, 132. 

" Zinc, 182. 
Lactic Acid, 133. 

Significance of, 517. 
Lead in Urine, 407. 
Leucin, 4, 147. 

" Elimination of when ingested, 206. 
" SiLmificance of, 516. 
Libnriiis's Method of Estimating Albumen, 298. 
Leibig's " " " Urea. 232. 

Lithium Salts in Urine, 196. 
Litmus. Eiiiiiination of when inge-ted, 209. 

Tincture of. 2.56. 
Liver, Acute Yellow Atrophy of, 4, 131, 153. 
" Cirrhosis of, Urophaein in. 365. 
" Organic Disease of, Case, 522. 
Logwood, Elimination of, 209. 

Madder, Elimination of, 209. 
Magnesium, Quantitative Estimation of, 802. 
" Significance of, 511. 

Phosphate, 83. 
Salts of in Urine, 198. 
Mandelic Acid, 198. 
Meliu's Method of Estimating Albumen, 298. 

Test for Albumen, 97. 
Melanaemia, 394. 
Melanogen, 368. 
Melanotic Cancer, .398. 
Meningitis, Specific Gravity of the Urine in, 

459. 
Mercuric Chloride, 16. 

" Cyanide, Standard Solution of, 265. 
Nitrate, 16. 

Standard Solution of, 233. 
Mercury in Urine, 192. 
Mesitylen, 203. 
Mesitylenic Acid, 203. 
Mesitylenuric Acid. 203. 
3Ietallic Compounds in LTrine, 193. 
Metasulphoplienate of Sodium, 204. 
Methagmoglobin, in Urine, 180. 

Significance of, 392. 
Methylglycocoll, 206. 
Methylhydantoic Acid, 206. 
Methylhydantoin, Influence of upon the Esti- 
mation of Urea, 241. 
Millon's Reagent, 93. 
Mineral Acids in Urine, 196. 
Mohr's Pipette, 227. 
Mohr-Westphal Balance, 213. 



INDEX, 



549 



Morphia, Elimination of, 208. 

Mucin, 175. 

Mucus in the Sediment, 175. 

" " ■' Significance of, 425. 

Mulberries, Influence of upon the LMne when 
ingested, 415. 

Mulberry Calculi, 53G. 

Mnrcxid, 39. 

Musk, Influence of upon the LMne when in- 
gested, 2U9. 

Naphthalin, 51. 
Nephrozjmose, 19, 97. 
Nephritis, Acute, Case of, 525. 
Neutral Reaciion of Urine, 377. 
Nickel in Urine, 408. 
Nitrate of Mercurv, 16, 233. 

" " Silver, Standard Sohttion of, 246. 

" " Urea, 17. 
Nitrates, 88. 

Nitric Acid Test for Albumen, 96, 379. 
Nitrite of Amyl, 102. 
Nitrites in Urine, 88. 
Nitrobenzoic Acid, 199. 
Nitrobenzol, 51, 102. 

Nitrogen, Quantitative Estimation of, 312. 
Nitrotoluol, 102, 203. 
Non-Oro;anized Sediments, 162, 410. 
Non- Volatile Salts, Quantitative Estunation of, 

221. 
Normal Constituents of Urine, 11. 
Normal Urine, Physical and Chemical Proper- 
ties of, 3. 

" " Reaction of, 6. 

" " Specitic Gravity of, 6. 

Odor of the Urine, 5, 369. 
Oil of Bitter Almonds, 198. 
Oils, Empyreumatic, Elimination of, 209. 
Omichmyloxid, 05. 
Omicholic Acid, 66. 

Optical Method of Estimating Albumen, 297. 
Organic Acids, Elimination of when ingested, 
198. 
" Bases, Elimination of when ingested, 

204. 
" Couipoundsof the Benzol Series, 202. 
" Salts, Elimination of wlien ingested, 
203. 
Organized Constituents of Urinary Sediment, 

175, 425. 
Osteomalacia, Earthy Phosphates in the Urine, 
514. 
" Paralactic Acid in the Urine, 

131. 
Oxalate of Calcium, 165. 

*' " '• Approximate Estimation 

of, 346. 
" " " Calculi, 536. 
"■ " " Significance of, 418. 
" Urea, 17. 
Oxalic Acid, Quantitative Estimation of, 321. 

Standard Solution of, 256. 
Oxaluric Acid, 42. 
Oxaluria, 420. 
Oxamide, 13. 
Oxindol, 69, 209. 
Oxybenzoic Acid, 199. 
Oxyhjemoglobin, 179. 
Oxymandel Acid, 153. 

" Significance of, 517. 

Oxyphenic Acid, 155. 

Palladium Chloride, Standard Solution of, 

279. 
Paraglobulln, 95, 99. 

" in Disease, 384. 

Paralactic Acid, 131. 
Paralbumen, 99. 

in Disease. .383. 
Paranltrobenzoic Acid. 203. 
Paranitrohippnric Acid, 203. 
Paranitrotoluol, 203. 



Paraoxj'benzolc Acid, 60, 199. 
Parasulphophenate of Sodium, 204. 
Peptone, 100. 

in Disease, 384. 
Peritonitis, Indicau in, 366. 
Peroxide of Hydrogen, 89. 
Peitenkofer's Tests lor Biliary Acids, 126. 
Phenol, 55,201. 
Phenylic Acid, 55, 201. 
Phosphate of the Alkoline Earths, 83. 
Phosphate of the Alkaline Earths, in the Sedi- 
ment, 168. 
Phosphate of the Alkaline Earths, in Rachitis 

514. 
Phosphate of the Alkaline Earths, Quantita- 
tive Estimation of, 299. 
Phosphate of Calcium, 83, 169. 
" Ma.^nesium, 8:3. 
"• " Sodium, Acid, 81. 

" " Urea, 18. 

Phosphatic Calculi, .537. 
Phosphoric Acid Analvsos, 349. 

"in tlie Fseces, 508. 
" " " ' Urine in Disease, 509. 

" " Quantitative Estimation of, 

250. 
" " Significance of, 504, 

" " Standard Solution of, 252. 

Phosphorus Poisoning, Urine in, lyi. 
Phthalic Acid, 51, 199^: 
Physical Properties of Normal Urine, 3. 
Picnometer, 214. 
Picric (Carbazotic) Acid, 51. 
Pigments, Biliary, 118, 398. 
Blood, 179, 392. 
" Urinary, Normal, 60, 363. 
" " Al)normal, 365. 

Accidental, 368. 
" " Significance of, 461. 

" " in Acute Febrile Diseases, 

464. 
Pipettes, 226. 

Piria's Test for Tyrosin, 150. 
Pneumonia, Case of, 5-22. 
Polarizer, Soleil-Ventzke, 267. 

Wikrs,271. 
Polyuria, 452. 

" Amount of Solids in, 456. 
Potassium in the Urine, 515. 

Quantitative Estimation of, 308, 310. 
" Acetate Solution for Preserving Uri- 
nary Sediments, 335. 
Bromide, 197. 
" Chloride, 79. 
" Ferrocyanide. 196. 
" " Standard Solution of, 

286. 
Iodide, 197. 
" " Standard Solution of, 279. 

Perchlorate, 197. 
" Permanganate, Standard Solution of, 

285. 
" Saccharate, 103. 
" Sulphate, Standard Solution of, 259. 
" Sulphocyanide, 196. 
tt " Standard Solution 

of, 249. 
" Urate, 164. ^, ,. ^ „„^ 

Preservative Fluids for Urinary Sediments, 334. 
Propionic Acid, 135. 
Propylbenzolc Acid, 20:. , ^, . 
Prunes, Influence of upon the Urnie when in- 
gested, 415. 
Pseudoxanthin, 39. 

Pulmonary Tuberculosis, Case ol, bZ6. 
Pus in the Sediment, 183. „ ,^ 

Donne's Test for, 184. 
(' " " Significance of, 4-28. 

Pus Corpuscles, Action of Acetic Acid on, 183. 
Pus Corpuscles, Action of Alkalies, on 184. 

Water on, 183. 
Pyrogallic Acid, 200. 



550 



INDEX. 



Qualitative Analysis of Urine, Systema- 
tic, 322. 
Quantitative Analysis of Urine, Systematic, 337. 
" " " Apparatus for, 

" " " General Rules 

for, 467. 
" Changes in the Urine, 443. 

" Determination of the Individual 

Substances, 225. 
" Estimation of the Acidity, 256. 

" '• " Albumen, 293. 

" " " Ammonia, 306. 

" '• " Biliary Acids, 

318. 
" " " Calcium, 299. 

" " " Carbonic Acid, 

312. 
" " " Chlorine, 245. 

" " " Coloring Mat- 

ters, 222. 
^' " " E.rthy Phos- 

phates. 299. 
" " " Fat, 318, 396. 

" " " Indican, 319. 

"■ " " Iodine, 278. 

" " " Iron, 285. 

" " " Kreatinin, 291. 

" " "■ Ma<j;nesium,302. 

" " " Nitrogen, 312. 

" " " Non-A^olatile 

Salts, 221. 
" " " Oxalic Acid, 321. 

" " " Phosphoric Acid, 

250. 
" " " Potassium, 308. 

" " " Potassium, and 

Sodium, 310. 
" " " Solid Residue, 

210. 
" Sugar, 261. 
'' " " Sulphuric Acid, 

2.57. 
" " " Urea, 232. 

" " " Uric Acid, 287. 

" Estimations, 210. 

" '• Approximate, 344. 

Quantity of the Urine, Estimation of. 210. 

" " " Variations in Health, 444. 

" " " Variations in Disease, 

451. 
Quinia, 204. 409. 
Quinic Acid, 198. 

Rachitis, Earthy Phosphates in, 514. 
Rautenl)erg's Method of Estimating Urea, 239. 
Reaction of Normal Urine, 6. 

" of the Urine, Alkaline, 377. 
" " " Amphigenous. 371. 

" " " Amphoterous, 371. > 

" " " Neutral, 377. 

" " " in Disease, 370. 

Renal Casts, 185. 

" " Significance of, 434. 
" " Epithelium, 427. 
" "■ Suppuration, 429. 
Residue of the Urine, Quantitative Estimation 
of, 216. 
" " " Estimation of from the 

Specific Gravity, 347. 
" " " Variations in Health,453. 

" " " " " Disease, 

455. 
Resins, 209. 
Rhubarb, 209, 368. 

Saccharate of Calcium, 103 

" Potassium, 103. 

Saccharimeter, Soleil-Ventzke, 267. 
Saccharimeter of Wild, 271. 
Saffron, Influence of upon the Urine when in^ 

gested, 209. 
Salicin, 51, 208. 



Saligenin, 208. 
Salicylic Acid, 199, 208. 
Hydride, 208. 
Salicyluric Acid, 51. 

Salkowski'sMethod of Estimating Uric Acid, 290. 
Salts of the Alkalies, 196. 

Alkaline Earths, 198. 
" " Ammonium, 86, 196. 
"" " Barium, 19s. 
" " Calcium, 198. 
" " Lithium, 196. 
" " Magnesium, 198. 
" " Potassium, 196. 
Santonin, 208, 368. 
Sap Green, 209. 

Sarcinie in the Sediment, 189, 439. 
Sarkin (Hypoxanthin), 33. 

" in the Sediment, 174. 
Sarkin, Significance of, 425. 
Sarkosin, Elimination of when ingested, 206. 
" Influence of upon the Estimation of 
Urea, 241. 
Scurvy, Hsemoglobinuria in, 392. 
Sediments, 159. 

" Significance of, 409. 

" Non-Organized, 162. 

Significance of ,410. 
" Organized, 175. 

" " Significance of, 425. 

" Preservation of, 334. 

" Systematic Examination of, 329. 

Sedimentum Lateritium, 159. 
Senna, Influence of upon the Urine when in- 
gested, 368. 
Silicic Acid, 88. 

Silver Nirrate, Standard Solution of, 246. 
Sodium Acetate, Standard Solution of, 252. 
Acid Phosphate, 81. 
'• and Potassium, Quantitative Estima- 
tion of, 310. 
" Benzol-Sulphate, 204. 
" Chloride, 76. 
" Ethereal Sulphates of, 204. 
" Hydrate, Standard Solution of, 256, 300, 

• 307, 314. 
'• Hypobromite, 16. 

HypobromitcStandard Solution of, 242, 
" Hypochlorite, 16. 
Urate, 164. 
Solid Residue, Estimation of, 216. 
" " " from the Specific 

Gravity, 347. 
" " Variations of, in Health, 4.53. 

" " '*' " Disease, 455. 

Specific Gravity of Normal Urine, 6. 
" Estimation of, 211. 
" Significance of, 453. 
Spectroscope, 181. 
Spermatozoa, 186. 

'• Significance of, 440. 

Spinal Diseases, Amount of Indican in, 366. 
Spores, 188, 4.38. 

Standard Solution of Barium Chloride, 2.58. 
'* " Copper Sulphate, 261. 

" " Hydrochloric Acid, 299. 

" " Mercuric Cvanide, 265. 

Nitrate, 233. 
" " Oxalic Acid, 2.56. 

" " Palladium Chloride, 279. 

" " Phosphoric Acid, 2.52. 

" " Potassium Ferrocyanide, 

286. 
" " Potassium Iodide, 279. 

" " Potassium Permanganate, 

285. 
" " Potassium Sulphate, 259. 

" " Potassium Sulphocyanide, 

249. 
Silver Nitrate, 246. 
" " Sodium Acetate, 2.52. 

" " " Hydrate, 256, 300 

307, 314. 



INDEX. 



551 



standard Solution of Sodium Hj'pobromite, 242. 
Sulphuric Acid, 306, 314. 
" " Uranium, 252. 

Urea, 233. 
Stercobilin, 64. 

Struve's Method of Estimating Iodine, 283. 
Strychuia, Elimination of, 208. 
Succinic Acid, 52, 200. 
Sugar, 101. 

Analj'ses, 350. 
" Approximate Estimation of, 402. 
" Bottger's (Bismuth i Test for, 106. 
" Quantitative Estimation of, by Circum- 

polarization, 266. 
" Quantitative Estimation of, by Fehling's 

Method, 261. 
" Quantitative Estimation of, by Fermen- 
tation, 276. 
" Quantitative Estimation of, by Knapp's 

Method, 2li5. 
" Significance of, 400. 
Sulphamic Acid, 206. 
bulphate of lodoquinine, 209. 

" Potassium. Standard Solution of, 259. 
Sulphates in Urine, 80. 
Sulphindigotic Acid, 72. 
Sulphocya'uide of Potassium, 196. 

" " Standard Solution 

of, 249. 
Sulphur Auratum Autimouii, 501. 
Sulphuretted Hydrogen, 142. 
Sulphuric Acid Aijalyses, 349. 

" " Quantitative Estimation of, 257. 

" " Standard solution of, 30li, 314. 

" " Variations of in Health, 4i)7. 

'■ Disease, 503. 
Suppuration of the Kidneys, 429. 
'• Ureters, 429. 
" Urethra, 429. 

Tannic Acid, Elimination of, 200. 

Tar as Cause of Dark Urine, 74, 369. 

Taurin, 124, 207. 

Taiirocarbainic Acid. 207. 

Taurocholic Acid, 124. 

Taurylic Acid, .57. 

Thallium in Urine, 195, 

Thein, 206. 

Theobromin, 206. 

Tohiic Acid, 199. 

Toluol, 203. 

Torula in the Sediment. 189, 438. 

Transfusion, Hsemoglobinuria following, 393. 

Transparency of the Urine. 370. 

Trichinosis, "Paralactic Acid in the Urine in, 131. 

Trimethylamin, 86. 

Trimethylbenzol, 203. 

Triple Pho.^pliate, 168. 

Calculi, 537. 
Trommer's Test for Suuar, 104. 
Tuberculosis. Puhnon;iry, Case of, 523. 
Tuberculous Masses in the Sediment. 430. 
Turnips, Influence of upon the Urine when 

ingested. 209. " 
Turpentine, 96, 102. 

" Influence of upon the Urine when 

ingested. 209. 
Typhoid Fever, Specific Gravity of the Urine in 

459. ' 

Tyrosin, 149. 

" Significance of, 516. 

" in the Sediment, 174. 

" " " Significance of, 424 

Uranium, Sandard Solution of, 252. 
Urate Sediments, 163. 

" " Significance of, 410. 

Urea, 11. 

" Elimination of when ingested, 206. 

" Influence of Age upon, 475. 
" Food '• 476. 

" Nitrate of. 17. 

" Oxalate of, 17. 



Urea, Phosphate of, 18. 
" Quantitative Estimation of, 232. 
" Standard Solution of. 233. 
" Variations of in Health, 473. 
" " " Disease, 477. 

Ureteritis. 429. 
Urethral Epithelium, 427. 
Urethritis, 429, 
Uric Acid, 35. 
" " Calculi, 533. 
" " Quantitative Estimation of, 287. 
" " Quantitative Estimation of , by Sal- 

kowski's Method, 290. 
" '• Sediment, 162, 41(J. 
" '• Variation of in Health, 481. 
" " " Disease, 482. 

Urina Chylosa. 14(1, 397. 
Urinary Calculi, 531. 

Casts. 185. 434. 
" Coloring Matters, 60, 363, 461. 
" Cous^tituents, Abnormal, 91, 378. 
" " Accidental, 190, 406. 

" " Inorganic, 76. 

" " Kormal, 11. 

" Fermentation. 7, 159. 
" Sediments, 1.59, 409. 
" " Non-Organized, 162, 410. 

" " Organized, 175, 425. 

" " Preservation of, 334. 

'• " Systematic Exam'n of, 329. 

Urine, Variations in the Amountof, in Disease, 

451. 
Urinometer, 211. 
Urobilin (Hydrobilirubin), 60. 

" Formation of, from HiBmoglobin, 64, 
464. 
Urochloralic Acid, 201. 
Urochrom, 64. 
Uroerythrin, 73. 368. 
Urofuscohtematin, 156. 
Uroglaucin, 68. 

'• in Disease, 367. 

Urohsematin, 65. 
Uromehmin. 66. 

Urophiein, Heller's Test for, 365. 
Uropittin, 66. 
Urorubroh.Tematin, 156. 
Uro.stealith Calculi, 535. 
Uroxanthin, 67. 

in Disease, 366. 
" Quantitative Estimation by Jaffe's 

Method, 319. 
Urrhodin, 65, 67. 

in Disease, 367. 

Valekian, Influence of upon the Urine when 
ingested, 2U9. 

Veratfia. Elimination of, 208, 

Vesical Hfemorrhoids, 390. 

Vibriones, 188. 

Violet Urine, 367. 

VogePs Optical Method of Estimating Albu- 
men, 29T. 

Volatile Fatty Acids, 134, 

Volumetric Analysis, 225. 

Watek, Action of on Pus Corpuscles, 183. 
Bath, 216. 
" Estimation of in Urine, 216. 
Wild's Poiaristrobometer, 271, 

Xanthin. 28. 

' Calculi, 534. 

" Sediment, 174. 

" " Significance of, 424. 

Xanthoproteic Acid, 92. 
Xylol, 203. 

Yeast Fungus. Sediment, 189. 
'• Spores, 439, 

Zinc in Urine, 408. 
" Chloride. Solution of, 291. 
" Lactate, 132. 



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